WO2012017502A1 - Organic electroluminescence element and method of manufacturing thereof - Google Patents

Organic electroluminescence element and method of manufacturing thereof

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Publication number
WO2012017502A1
WO2012017502A1 PCT/JP2010/004992 JP2010004992W WO2012017502A1 WO 2012017502 A1 WO2012017502 A1 WO 2012017502A1 JP 2010004992 W JP2010004992 W JP 2010004992W WO 2012017502 A1 WO2012017502 A1 WO 2012017502A1
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WO
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layer
hole
injection
tungsten
organic
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PCT/JP2010/004992
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French (fr)
Japanese (ja)
Inventor
原田 健史
西山 誠司
小松 隆宏
竹内 孝之
慎也 藤村
大内 暁
藤田 浩史
義朗 塚本
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パナソニック株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED];
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED];
    • H01L51/5088Carrier injection layer
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED];
    • H01L51/56Processes or apparatus specially adapted for the manufacture or treatment of such devices or of parts thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2251/00Indexing scheme relating to organic semiconductor devices covered by group H01L51/00
    • H01L2251/50Organic light emitting devices
    • H01L2251/53Structure
    • H01L2251/5369Nanoparticles used in whatever layer except emissive layer, e.g. in packaging
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L27/00Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/28Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including components using organic materials as the active part, or using a combination of organic materials with other materials as the active part
    • H01L27/32Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including components using organic materials as the active part, or using a combination of organic materials with other materials as the active part with components specially adapted for light emission, e.g. flat-panel displays using organic light-emitting diodes [OLED]
    • H01L27/3241Matrix-type displays
    • H01L27/3244Active matrix displays
    • H01L27/3246Banks, i.e. pixel defining layers

Abstract

Provided is an organic electroluminescence element that has adopted a hole injection layer with which a favorable hole-conducting efficiency can be achieved. The organic electroluminescence element is provided with: a functional layer (6) composed of 1 or more layers, arranged between an anode (2) and a cathode (8), and comprises a light-emitting layer (6B) constituted by using an organic material; a hole injection layer (4) arranged between the anode (2) and the functional layer (6); and banks (5) that prescribe the light-emitting layer (6B). The hole injection layer (4) contains tungsten oxide therein, and the tungsten element constituting the tungsten oxide is contained in the hole injection layer (4) in hexavalent state, or in a state having ionic valence lower than the hexavalent state, and the hole injection layer (4) also contains therein tungsten oxide crystals the particle diameter of which is in the order of nanometers. The hole injection layer (4) is formed to have, in a section prescribed by the banks (5), a reentrant structure wherein a portion of the surface of the functional layer (6) side thereof is positioned more to the anode (2) side than the other portions, and the inner faces of the recess section in this reentrant structure are in contact with the functional layer (6).

Description

The organic EL device and a manufacturing method thereof

The present invention relates to an electrical light emitting device in which organic electroluminescent elements (hereinafter referred to as "organic EL device") and a manufacturing method thereof, particularly to a technique for improving the hole conduction efficiency in the hole injection layer.

Recently, research and development of various functional elements using an organic semiconductor has been advanced, the organic EL element can be cited as typical functional elements. The organic EL element is a light emitting element of a current drive type, having a structure in which a functional layer including a light emitting layer made of an organic material between a pair of electrode pair consisting of an anode and a cathode. Then, a voltage is applied between the electrode pairs, are injected into the functional layer from the hole and a cathode are injected into the functional layer from the anode are recombined and an electron, thereby emitting light by electroluminescence phenomenon occurring. The organic EL element is excellent in vibration resistance for visibility for performing self-luminous is higher and solid-state devices, utilized as a light emitting element and a light source in various display devices have attracted attention.

The organic EL element to emit light with high brightness, it is important to inject efficiently carrier from the electrode to the functional layer (holes and electrons). In general, in order to inject better carrier efficiency, between each electrode and the functional layer, it is effective to provide an injection layer for a low energy barrier during injection. The hole injection layer disposed between the one functional layer and the anode, organic material such as copper phthalocyanine and PEDOT (conductive polymer), a metal oxide such as molybdenum oxide or tungsten oxide is used. Further, the functional layer and the electron injecting layer disposed between a cathode, organic material such as a metal complex or oxadiazole, metals such as barium are used.

Among them, with respect to the organic EL element using a metal oxide film made of a metal oxide such as molybdenum oxide or tungsten oxide as a hole injection layer, the improvement of improvement and lifetime of the hole conduction efficiency have been reported (Patent Document 1, 2, non-patent document 1).

JP 2005-203339 JP JP 2007-288074 JP

Jingze Li et al. , Synthetic Metals 151,141 (2005). M. Stolze et al. , Thin Solid Films 409, 254 ( 2002) Kaname Kanai et al., Organic Electronics 11,188 (2010). I. N. Yakovkin et al. , Surface Science 601,1481 (2007).

As a method of forming the metal oxide film, a vapor deposition method or sputtering method is generally used. In this case, considering the heat resistance of the layer such as a metal oxide film is formed previously on the substrate at the time it is deposited, typically, the deposition of the metal oxide film at a low temperature of the substrate temperature of 200 ° C. or less It is being carried out.

When performing film formation at a low substrate temperature in the sputtering method, since the thermal energy generated when the film forming gas reaches the deposition substrate is absorbed quickly into the deposition substrate, the orderliness less amorphous structure metal liable oxide film is formed. Furthermore, when a film was formed at a low substrate temperature, that retains the uniformity of the film composition and film thickness has also been reported to be difficult (Non-Patent Document 2).

If the metal oxide film is an amorphous structure, site of contributing to the conduction holes injected into the metal oxide film, for example, for sites like oxygen defects are scattered, row by mainly hopping conduction conduction of holes divide. The hopping conduction, but between the hole conducting portion between interspersed holes hopping, this in order to utilize the driving of the organic EL element, it is necessary to apply a high driving voltage to the organic EL element, as a result, there is a problem in that hole conduction efficiency is low.

The present invention was made in view of the above problems, and an object thereof is to provide an organic EL device employing a hole injection layer excellent hole conduction efficiency.

To achieve the above object, the organic EL device according to an embodiment of the present invention includes an anode, a cathode, is disposed between the anode and the cathode, the light-emitting layer made of an organic material, one or comprising a functional layer composed of a plurality of layers, a hole injection layer disposed between the anode and the functional layer, and a bank defining the light-emitting layer, the hole injection layer comprises a tungsten oxide, the tungsten elements constituting the tungsten oxide is contained in the hole injection layer at a lower valence state than hexavalent state and the hexavalent and the hole injection layer, the particle size of nanometer order size wherein said tungsten oxide crystal is, the in banks defined area is formed on the recessed structure in which a part of the surface of the functional layer side is positioned on the anode side than the other portions, the recessed to structure The inner surface of the kick recess, characterized in that in contact with the functional layer.

In the organic EL device according to an embodiment of the present invention is to constitute the hole injection layer by tungsten oxide, tungsten elements constituting the tungsten oxide, the lower valence state than hexavalent state and the hexavalent it is, can have a structure similar to the oxygen defect which is a conductive portion of the hole to the hole injecting layer. Further, the crystal grain size of the tungsten oxide by the size of the nanometer order, concomitantly, crystal grain boundary structure similar to oxygen defects exist many are many formed on the hole injection layer. This makes it possible to stretch around the hole conductive path in the thickness direction of the hole injection layer, it is possible to achieve efficient hole conduction at a low driving voltage.

In the case where the hole injection layer is composed of tungsten oxide there are many structures similar to the above oxygen defects, the thickness of the hole injection layer decreases in the manufacturing process, results in a so-called film reduction problem, defined by the bank by lowering the like brightness variation and device life in the light emitting portion plane of the region, it may affect the emission characteristics.

In contrast, in one embodiment of the organic EL device of the present invention described above, formed as a hole injection layer, forming a recess structure in which a part of the surface of the functional layer side is positioned closer to the anode than the other surface portion It is. Further, the inner surface of the recess of the hole injection layer (bottom and side surfaces) are formed such functional layer is in contact. This improves the wettability of the functional layer to the hole injection layer, even if caused a hole injection layer film reduction can be favorably formed an element with high definition patterning by preventing uneven application of the functional layer material. Therefore, it is possible to prevent the occurrence of problems such as reduction of the brightness variation and device life, to prevent the occurrence of influence on light emitting property in advance.

(A) a schematic cross-sectional view showing a structure of an organic EL element 1000 according to the first embodiment and is a partial enlarged view of the vicinity of (b) a hole injection layer 4. It is a schematic sectional view showing a structure of a Hall-only element 1000A. A device characteristic diagram showing the relationship curve between the applied voltage and the current density of the Hall-only device. A device characteristic diagram showing the relationship curve between the applied voltage and the current density of the organic EL element. W5p 3/2, W4f 5/2 by XPS measurement of the tungsten oxide layer surface is a diagram showing a spectrum attributed to W4f 7/2. (A) and shows a peak fitting analysis results of the sample A shown in FIG. 5 is a diagram showing a peak fitting analysis results according to (b) Sample E. It is a diagram illustrating a UPS spectrum of the tungsten oxide layer. It is a diagram illustrating a UPS spectrum of the tungsten oxide layer. It is a diagram for explaining the structure of the tungsten oxide layer. Is a TEM photograph of the tungsten oxide layer section. It is a diagram showing a two-dimensional Fourier transform image of the TEM photograph shown in FIG. 10. Is a diagram illustrating a process of creating a luminance change plot from the two-dimensional Fourier transform image shown in FIG. 11. Samples A, B, and Fourier transform image in C, it is a diagram illustrating a change in luminance plot. A Fourier transform image of the sample D, E, it is a diagram illustrating a change in luminance plot. Sample A, Sample E luminance change plot ((a), (b)) and an enlarged view of the vicinity of the peak of the normalized luminance appearing closest to the center point of each luminance change plot ((a1), (b1)) When a diagram showing a first derivative of the plot of (a1) and (b1) ((a2), (b2)). Tungsten oxide layer is a diagram schematically showing a diagram schematically showing the hole conductive when it is (b) an amorphous structure hole conductive when it is (a) nanocrystals structure. A device characteristic diagram showing the relationship curve between the applied voltage and the current density of the Hall-only device. It is a graph showing the relationship between the film thickness reduction amount and the film density of the tungsten oxide layer constituting the hole injection layer. It is a schematic diagram illustrating the relationship between the film structure and the film density of the tungsten oxide layer constituting the hole injection layer. It is a schematic view showing a stacked state of the layers of the organic EL device 100 according to the second embodiment. Is an enlarged view of a portion surrounded by a one-dot chain line in FIG. 20. It is an enlarged view of a portion surrounded by a one-dot chain line in FIG. 20 of the organic EL device according to a modification of the second embodiment. It is an enlarged view of a portion surrounded by a one-dot chain line in FIG. 20 of the organic EL device according to a modification of the second embodiment. It is a schematic diagram for explaining the optimum thickness of the light-emitting layer. It is an enlarged view of a portion surrounded by a one-dot chain line in FIG. 20 of the organic EL device according to a modification of the second embodiment. It is a process diagram illustrating a method of manufacturing an organic EL element according to the second embodiment. It is a process diagram illustrating a method of manufacturing an organic EL element according to the second embodiment following FIG 26. It is a schematic view showing a stacked state of the layers of the organic EL device 100A according to the third embodiment. It is a process diagram illustrating a method of manufacturing an organic EL element according to the third embodiment. It is a schematic view showing a stacked state of the layers of the organic EL device 100B according to the fourth embodiment. It is a process diagram illustrating a method of manufacturing an organic EL element according to the fourth embodiment. It is a perspective view showing a display device or the like according to the fifth embodiment.

[Aspects of the implementation]
The organic EL device according to an embodiment of the present invention comprises an anode, a cathode, is disposed between the anode and the cathode, including a light emitting layer formed using an organic material, functional layer comprising one or more layers If, comprising a hole injection layer disposed between the anode and the functional layer, and a bank defining the light-emitting layer, the hole injection layer comprises a tungsten oxide, a tungsten element forming the tungsten oxide is included in the hole injection layer at a lower valence state than hexavalent state and the hexavalent and the hole injection layer, the particle size of the tungsten oxide is a size of nanometer order crystal hints, the in defined region in the bank is formed in a recessed structure portion of the surface of the functional layer side is positioned on the anode side than the other portions, the edge of the recess in the recess structure wherein van It has a configuration which is coated with a part of.

In the organic EL device according to an embodiment of the present invention is to constitute the hole injection layer by tungsten oxide, tungsten elements constituting the tungsten oxide, the lower valence state than hexavalent state and the hexavalent it is, can have a structure similar to the oxygen defect which is a conductive portion of the hole to the hole injecting layer. Additionally, the crystal grain size of the tungsten oxide by the size of the nanometer order, concomitantly, crystal grain boundary structure similar to oxygen defects larger amount is a number formed on the hole injection layer. This makes it possible to stretch around the hole conductive path in the thickness direction of the hole injection layer, it is possible to achieve efficient hole conduction at a low driving voltage. Here, the "size of nanometer order," which refers to the size of about 3 ~ 10 nm, and less than the thickness of the hole injection layer.

In the case where the hole injection layer is composed of tungsten oxide there are many structures similar to the above oxygen defects, the thickness of the hole injection layer decreases in the manufacturing process, results in a so-called film reduction problem, defined by the bank by lowering the like brightness variation and device life in the light emitting portion plane of the region, it may affect the emission characteristics. In contrast, in one embodiment of the organic EL device of the present invention described above, formed as a hole injection layer, forming a recess structure in which a part of the surface of the functional layer side is positioned closer to the anode than the other surface portion It is. Further, the inner surface of the recess of the hole injection layer (bottom and side surfaces) are formed such functional layer is in contact. This improves the wettability of the functional layer to the hole injection layer, even if caused a hole injection layer film reduction can be favorably formed an element with high definition patterning by preventing uneven application of the functional layer material. Therefore, it is possible to prevent the occurrence of problems such as reduction of the brightness variation and device life, to prevent the occurrence of influence on light emitting property in advance.

Here lower valence than the hexavalent may be that it is pentavalent. Further, the number of atoms pentavalent tungsten element, may be the hexavalent atoms divided by the value at which W 5+ / W 6+ tungsten elements is 3.2% or more. To hexavalent tungsten atom can be pentavalent tungsten atoms it contains more than 3.2%, to obtain a better hole conduction efficiency.

Moreover, even said W 5+ / W 6+ is 7.4% less than 3.2%, it is possible to obtain better hole conduction efficiency.

In the hard X-ray photoelectron spectrum of the hole injection layer surface, lower binding energy region than the first peak corresponding to the 4f 7/2 level of hexavalent tungsten, in other words the second peak exists in a shallow energy level it is also possible to be. The second peak specifically, may be present in the 0.3 ~ 1.8 eV lower binding energy region than the binding energy value of the first peak. The first peak corresponds to the peak of hexavalent tungsten atoms, one of the second peak, corresponding to the peak of the pentavalent tungsten atoms.

Area intensity of the second peak, relative to the integrated intensity of the first peak, may be from 3.2 to 7.4%. The ratio of the area of ​​the first peak and the second peak corresponds to the abundance ratio of hexavalent tungsten atoms and pentavalent tungsten atoms. That is, for hexavalent tungsten atoms, which indicates that the pentavalent tungsten atoms are contained at a ratio of 7.4% or less than 3.2%.

The presence of lower tungsten element than the maximum valence, to have occupied level to 1.8 ~ 3.6 eV lower binding energy region than the lowest binding energy valence band in the hole injection layer it may be. By this occupation levels are present, it is possible to reduce the hole injection barrier between the hole injection layer and the functional layer. As a result, it is possible to obtain a better hole injection efficiency. Here, "the lowest binding energy in the valence band" means the energy corresponding to the position of the top of the valence band from the vacuum level.

Further, the hole injection layer, a particle size includes a plurality of crystals of 3 to 10 nanometers in size is the tungsten oxide, the lattice image by transmission electron microscopy of the hole injection layer section, 1 .85 may be linear structures are arranged regularly at intervals of ~ 5.55A appears. In TEM photograph of particle size 3-10 nm in size the tungsten oxide layer surface which crystals contained in, by partially bright portion are arranged in the same direction, regularly arranged linear structure appears. The regular linear structure suggests the existence of crystals of nanometer order.

Further, in the two-dimensional Fourier transform image of the grating image, it is also possible to concentric pattern around the center point of the two-dimensional Fourier transform image appears. When crystals of nanometer order is present, concentric pattern as described above appears accordingly.

Further, the distance from the center point, the plot representing the relationship between the normalized luminance intensity of the two-dimensional Fourier transform image is a numerical value normalized in the distance, the peak of the normalized luminance appears one or more it may be. Peak one of normalized luminance in the plot corresponds to one of the concentric pattern.

Closest to appear corresponding to the position of the peak of the normalized luminance the distance and the difference between the distance corresponding to the rising position of the peak of the normalized luminance as a peak width, the center from the center point in the plot and said distance corresponding to the point may be smaller than the peak width is 100 the difference between the distance corresponding to the peak of the normalized luminance appearing closest from the center point 22. The most central peak of the normalized luminance appearing near distance point corresponds to concentric pattern based on the presence of crystals of nanometer order. Also, the more the abundance of crystals of nanometer order, the half width is less of a peak of the normalized luminance, i.e., the width of the normalized luminance becomes smaller. It can peak width that crystals of nanometer order is present to the extent that within a predetermined range, obtaining better hole conduction efficiency.

The functional layer may be that it contains an amine-based material. In the organic molecules of amines, since the electron density of the HOMO around the unshared electron pair of the nitrogen atoms are distributed, this portion becomes the injection site of the hole. By functional layer contains an amine-based materials, it is possible to form the injection site of the hole in the functional layer side, can be efficiently inject holes that have been conducted from the hole injection layer in the functional layer and Become.

The functional layer, the hole transport layer for transporting holes, may be any of the buffer layer used in applications adjustment or electron blocking optical properties.

The bank is lyophobic, it may be the hole injection layer is lyophilic.

The organic EL panel according to the present invention, the organic EL light-emitting device, an organic EL display device includes an organic EL element having the above structure. This makes it possible to configure an organic EL panel that the same effect as described above can be obtained, the organic EL light-emitting device, an organic EL display device.

The method for manufacturing an organic EL device according to an embodiment of the present invention comprises an anode preparation step of preparing an anode, a tungsten oxide film forming step of forming a tungsten oxide layer on the anode, argon gas and oxygen gas sputtering gas composed, and, using a target made of tungsten, the with the total pressure of the sputtering gas is less than 7.0Pa than 2.3Pa, the ratio of the oxygen gas partial pressure to the total pressure of the sputter gas is more than 50% is 70% or less, and the input power density is closing electric power per unit area of the target is at 1.5 W / cm 2 or more 6.0 W / cm 2 or less, and put the total pressure of the sputtering gas oxide tungsten to the total pressure / input power density which is a value obtained by dividing the power density is deposited tungsten oxide layer at a greater deposition conditions than 0.7 Pa · cm 2 / W And Ten film forming step, over the tungsten oxide layer, a resist film is formed comprising a resist material, etching treatment with a developer, a bank forming step of forming a bank, after forming the banks, the tungsten oxide layer the resist residues adhering to the surface as well as washing with a cleaning solution, the cleaning solution in dissolving a portion of the tungsten oxide layer, a portion of the top surface is positioned on the anode side than the other portions of the upper surface, and an inner bottom surface a hole injection layer forming step of forming a hole injection layer having a concave portion having an inner surface that is continuous with said bottom surface, the ink was dropped within a defined region by the bank, the inner surface of the recess of the hole injection layer the ink coating to dry in contact with, the functional layer forming step of forming a functional layer, a cathode forming step of forming the cathode above the functional layer It has a.

The manufacturing method of the organic EL device according to an embodiment of the present invention comprises an anode preparation step of preparing an anode, a tungsten oxide film forming step of forming a tungsten oxide layer on the anode, argon gas and oxygen sputtering gas consisting of a gas, and, using a target made of tungsten, with total pressure is less than 7.0Pa or 2.3Pa of the sputtering gas, the ratio of the oxygen gas partial pressure to the total pressure of the sputtering gas is 50 % or more and 70% or less, and input power density is closing electric power per unit area of the target is at 1.5 W / cm 2 or more 6.0 W / cm 2 or less, and the total pressure of the sputtering gas total pressure / input power density which is a value obtained by dividing the in input power density is deposited tungsten oxide layer at a greater deposition conditions than 0.7 Pa · cm 2 / W oxide capacitor A tungsten deposition process, above the tungsten oxide layer, resist residues resist film is formed comprising a resist material, etching treatment with a developer, to form a bank, adhere to the tungsten layer surface by the developer washed, and, by the washing liquid to dissolve a portion of the tungsten oxide layer, inner portion of the upper surface than other portions of the upper surface located on the anode side, continuous to the inner bottom surface and the inner bottom surface a hole injection layer forming step of forming a hole injection layer having a concave portion and a side surface, the ink was dropped into area already defined by the bank, so as to contact the ink in the inner surface of the concave portion of the hole injection layer applied to dried, a functional layer formation step of forming a functional layer, above the functional layer, as having a cathode forming step of forming the cathode Good.

Further, in the tungsten oxide film forming step, the tungsten element forming the tungsten oxide layer is, the tungsten oxide layer to the maximum valence state and the maximum valence lower valence than the number of states in which the tungsten element may take to include, and, as the particle size is contained crystals of tungsten oxide is the size of the nanometer order, it is also possible to deposit the tungsten oxide layer. Further, the tungsten oxide film formation step, the total pressure / input power density may be less than 3.2Pa · cm 2 / W. By going through these processes, it is possible to form the organic EL element same effect as described above can be obtained.

[Embodiment 1]
<Structure of the organic EL element>
1 (a) is a schematic sectional view showing a structure of an organic EL element 1000 according to this embodiment, FIG. 1 (b) is a partially enlarged view of the vicinity of the hole injection layer 4.

The organic EL element 1000, for example, the functional layer a coating type which is prepared by coating by a wet process, the hole injection layer 4, various functional layers comprising an organic material having a predetermined function are stacked together state, having interposed configurations between electrode pair comprising an anode 2 and cathode 8.

As shown in FIG. 1 in particular, the organic EL element 1000 (an example of a functional layer) on one side main surface of the substrate 1, an anode 2, ITO layer 3, the hole injection layer 4, the buffer layer 6A, the light-emitting layer (an example of a functional layer) 6B, the electron injection layer 7, and the cathode 8, the sealing layer 9 are laminated in this order.

(Substrate 1, an anode 2, ITO layer 3)
Substrate 1 is a portion serving as a base material of the organic EL element 1000, for example, alkali-free glass, soda glass, nonfluorescent glass, phosphate glass, borate-based glass, quartz, acrylic resin, styrene resin, polycarbonate resin , it is possible to form an epoxy resin, polyethylene, polyester, either silicone resin or insulating material such as alumina.

Although not shown, the surface of the substrate 1 TFT for driving the organic EL element 1000 (thin film transistor) is formed, the anode 2 is formed on its upper side. The anode 2 may, for example, APC (silver, palladium, copper alloy), ARA (silver, rubidium, gold alloy), MoCr (molybdenum and chromium alloy), NiCr can be formed by (a nickel and chromium alloy), etc. can.

ITO layer (indium tin oxide) 3 has a function interposed between the anode 2 and the hole injection layer 4, to improve the bonding of the layers.

(Hole injection layer 4)
Hole injection layer 4 is, for example, a tungsten oxide layer having a thickness of 30 nm (WOx). Tungsten oxide, in its composition formula WOx, a real number in the range of x is approximately 2 <x <3. Although it is desirable constituted only by the hole injection layer 4 is possible tungsten oxide, to the extent that may be incorporated in the normal level, it may contain trace amounts of impurities.

Here, the tungsten oxide layer is deposited at a predetermined film deposition conditions. The details for a given deposition conditions are described in detail in the section of (Manufacturing method of the organic EL element 1000) and (film forming conditions for hole injection layer 4). By tungsten oxide layer is deposited at the predetermined deposition conditions, as shown in FIG. 1 (b), tungsten oxide layer contains a large number of crystal 13 of tungsten oxide. The particle size of each crystal 13 is formed to have a size of nanometer order. For example, for a thickness of 30nm about a hole injection layer 4, the particle size of the crystal 13 is about 3 ~ 10 nm. Hereinafter, particle size refers to the crystal 13 size of nanometer order as "nanocrystals 13", the structure of a layer composed of nanocrystals 13 is referred to as "nanocrystals structure". Incidentally, in the hole injection layer 4, in a region other than the region where taking the nanocrystals structure, amorphous structure are also included.

In the hole injection layer 4 having a nanocrystal structure as described above, tungsten atoms constituting the tungsten oxide (W) has a lower valence state than the maximum valence state and the maximum valence of tungsten can take It is distributed so. In general, the crystal structure of the tungsten oxide is not uniform, include structures similar to oxygen defects. Among them, in the tungsten oxide crystal structure having no structure similar to the oxygen defects, the maximum valence of possible tungsten is hexavalent state. On the other hand, in the tungsten oxide crystal structure having a structure similar to the oxygen defects, the valence of tungsten have been found to be 5 valence state lower than the maximum valence. Incidentally, the film of tungsten oxide, the maximum valence of the maximum value lower valence than the number or the like is constituted gathered tungsten atoms of different valence states, when viewed in the entire film, their and it has a valence of the average of the various valence.

Here, by taking a structure similar to the oxygen defect, the electron level based on the structure, it has been reported that hole conduction efficiency is increased (Non-Patent Document 3). Further, as described in FIG. 9, the structure similar to the oxygen defects are found to be abundant in the surface of the crystal.

Accordingly, in a tungsten oxide, tungsten are distributed so as to have a hexavalent or pentavalent state, by providing a structure similar to the oxygen defects in the hole injection layer 4, it views the improvement of hole conduction efficiency. That is, since the holes supplied from the anode 2 to the hole injection layer 4 conducts oxygen defects existing in the crystal grain boundary, the tungsten oxide layer by a nanocrystal structure, it is possible to increase the path holes are conducted , it leads to an improvement in hole conduction efficiency. Therefore, it is possible to lower the driving voltage to start the organic EL element 1000.

Further, the hole injection layer 4 is chemically resistant is high, that is composed of a hard tungsten oxide cause unwanted chemical reactions. Accordingly, the hole injection layer 4, even when the contact with a solution or the like used in the process or the like performed after the formation of the same layer, dissolution, alteration, it is possible to suppress damage to the hole injection layer 4 by decomposition . Thus, the hole injection layer 4 is, by chemical resistance is formed by a high material, it is possible to prevent a decrease in hole conduction performance of the hole injection layer 4.

Hole injection layer 4 in this embodiment, the case that consists only of tungsten oxide nanocrystals structure, when configured from both the tungsten oxide of the tungsten oxide and the amorphous structure of the nanocrystal structure, both It is intended to include. Also, nanocrystals structure is desirably present throughout the hole injection layer 4, the interface anode 2 and the hole injection layer 4 are in contact with one location between the interface hole injection layer 4 and the buffer layer 6A is in contact But if connected grain boundaries, it is possible to conduct the holes into the upper end from the lower end of the hole injection layer 4.

The example itself using tungsten oxide layer containing crystallized tungsten oxide as a hole injection layer has been reported in the past. For example, Non-Patent Document 1, hole conductivity has been shown to improve by crystallizing tungsten oxide layer by annealing 450 ° C.. However, including the effect on other layers such as a substrate hole injection layer Non-Patent Document 1 is deposited, not shown for the bear practicality in mass production of large-sized organic EL panel. Furthermore, not been shown to form a nanocrystal of tungsten oxide having a positively oxygen defects in the hole injection layer. Hole injection layer according to an embodiment of the present invention does not easily cause a chemical reaction, it is stable, and a tungsten oxide layer to withstand mass production process of a large organic EL panel. Further, by the presence of positively oxygen defects in the tungsten oxide layer, in that it provides excellent hole conductivity and hole injection efficiency, in which the prior art differ.

(Bank 5)
On the surface of the hole injection layer 4, an insulating organic material (e.g., acrylic resin, polyimide resin, novolac-type phenol resin) bank 5 made of, so as to form a stripe structure or parallel crosses structure with a constant trapezoidal section It is formed on. The partition surface of the hole injection layer 4 in each bank 5, a buffer layer 6A, red (R), green (G), and a light emitting layer 6B corresponding to one color of blue (B) Function layers are formed. As shown in FIG. 1, the organic EL element 1000 in the case of application to the organic EL panel, a series of three elements 1000 corresponding to each color of RGB on the substrate 1 as one unit (pixel, pixels), which is more It is juxtaposed over the unit.

Incidentally, the bank 5 is not essential to the present invention, it is unnecessary when such use of organic EL elements 1000 by itself.

(Functional layer 6)
The organic EL element 1000 in addition to the hole injection layer 4, required for the organic EL element 1000, the functional layer is present to fulfill the required function. Functional layer in the present invention, the hole-transporting layer for transporting holes, either the injected holes and electrons emitting layer which emits light by recombination of the buffer layer and the like used in applications adjustment or electron blocking optical properties or, or it refers to a layer that contains all of the layers of two or more layers of the combined layer or these layers. In this embodiment, as the functional layer 6, an example including the buffer layer 6A and the light-emitting layer 6B.

Buffer layer 6A is, for example, an amine-based organic polymer having a thickness of 20nm TFB (poly (9,9-di-n-octylfluorene-alt- (1,4-phenylene - ((4-sec-butylphenyl) imino ) -1,4-phenylene)) it is composed of.

By forming the buffer layer 6A with an amine-based organic molecules, the holes that have been conducted from the hole injection layer 4, it is possible to efficiently inject the functional layer formed on the upper layer from the buffer layer 6A. That is, in the organic molecules of the amine, since the electron density of the HOMO around the unshared electron pair of the nitrogen atoms are distributed, this portion becomes the injection site of the hole. By the buffer layer 6A contains an amine-based organic molecules, it is possible to form the injection site of the hole in the buffer layer 6A side.

Emitting layer 6B, for example, composed of an organic polymer having a thickness of 70nm F8BT (poly (9,9-di-n-octylfluorene-alt-benzothiadiazole)). However, the light emitting layer 6B is not limited to the structure made of this material, it is possible to configure to include known organic materials. For example oxinoid compounds described in JP-A-5-163488, perylene compounds, coumarin compounds, Azakumarin compounds, oxazole compounds, oxadiazole compounds, perinone compound, pyrrolo-pyrrole compounds, naphthalene compounds, anthracene compounds, fluorene compounds, fluoranthene compounds, tetracene compounds, pyrene compounds, coronene compounds, quinolone compounds, and azaquinolone compounds, pyrazoline derivatives and pyrazolone derivatives, rhodamine compounds, chrysene compounds, phenanthrene compounds, cyclopentadiene compounds, stilbene compounds, diphenyl quinone compounds, styryl compounds, butadiene compounds, dicyanomethylenepyran compounds, dicyanomethylenethiopyran compound, fluorescein compound, pyrylium compounds, Apiririumu compounds, Serena pyrylium compounds, telluropyrylium compounds, aromatic Arudajien compounds, oligophenylene compounds, thioxanthene compounds, cyanine compounds, acridine compounds, metal complexes of 8-hydroxyquinoline compounds, metal complexes of 2-bipyridine compound, a Schiff salt complexes of group III metals, oxine metal complexes can include a fluorescent substance such as rare earth complex.

(Electron injection layer 7 to cathode 8, the sealing layer 9)
Electron injection layer 7 has a function of transporting electrons injected from the cathode 8 to the light-emitting layer 6B, for example, it is formed with barium having a thickness of about 5 nm, phthalocyanine, lithium fluoride, or a combination thereof layer it is preferable.

Cathode 8, for example, a thickness of 100nm approximately aluminum layer. The anode 2 and cathode 8 described above DC power source is connected, and is powered to the organic EL element 1000 from outside.

The sealing layer 9, or the like emitting layer 6 is exposed to moisture, has a function of suppressing it or exposed to air, for example, SiN (silicon nitride), a material such as SiON (silicon oxynitride) It is formed. For top emission type organic EL device, it is preferably formed of a light transmissive material.

<Outline of the manufacturing method of the organic EL element 1000>
Next, to illustrate the overall manufacturing process of the organic EL element 1000 in accordance with the present embodiment based on FIG.

First, placing the substrate 1 into the chamber of the sputtering apparatus. And introducing a predetermined sputtering gas into the chamber, forming the anode 2 on the basis of the reactive sputtering method. Incidentally, the anode 2 may be formed by vacuum deposition or the like. Subsequently, within the above chamber, an ITO layer 3 on the anode 2 on the basis of the sputtering.

Next, forming the hole injection layer 4, it is preferable that a film is formed by reactive sputtering. Specifically, the metal tungsten as a target, an argon gas as a sputtering gas, is introduced into the chamber oxygen gas as a reactive gas. The high voltage in this state with argon to ionize, thereby collide with the target. The metal tungsten, which is emitted by sputtering phenomenon reacts with oxygen gas becomes tungsten oxide, tungsten oxide layer is deposited on the ITO layer 3.

Although described in the next section for more information on the film forming conditions, Briefly, (1) total pressure of the sputtering gas composed of argon gas and oxygen gas is not more than 7.0Pa than 2.3Pa, and , (2) oxygen gas partial pressure to the total pressure of the sputtering gas is 70% or less than 50%. And (3) closing electric power per unit area of the target (input power density) is at 1.5 W / cm 2 or more 6.0 W / cm 2 or less, and (4) the total pressure of the sputtering gas in the input power density it is preferred that the total pressure / power density is divided by the value is set to be larger than 0.7Pa · cm 2 / W. Such deposition conditions, the tungsten oxide film is formed having a nanocrystal structure.

As described above, tungsten oxide constituting the hole injection layer 4 has a high chemical resistance. Accordingly, the hole injection layer 4, even when the contact with a solution or the like used in the subsequent step, dissolution, alteration, it is possible to suppress damage to the hole injection layer 4 by decomposition.

Then, as the bank material, for example, photosensitive resist material, preferably providing a photoresist material containing a fluorine-based material. The bank material was uniformly applied on the hole injection layer 4, prebaked, superimposed a mask having openings of a predetermined shape (pattern bank to be formed). Then, after the photosensitive from over the mask, wash out excess bank material uncured with a developer. Finally, the bank 5 is completed by washing with pure water.

Next, the surface of the hole injection layer 4, for example, by a wet process by a spin coating method, an inkjet method, was added dropwise a composition ink containing the amine-based organic molecular material, thereby the solvent removed by volatilization. Thus the buffer layer 6A is formed.

Next, the surface of the buffer layer 6A, in a similar manner, was added dropwise a composition ink containing the organic luminescent material, thereby the solvent removed by volatilization. Thus the light emitting layer 6B is formed.

The buffer layer 6A, the method of forming the light emitting layer 6B is not limited thereto, a method other than spin coating method, an inkjet method, for example, a gravure printing method, a dispenser method, a nozzle coating method, intaglio printing, known relief printing such as ink may be dropping and coating by the method.

Subsequently, an electron injection layer 7 by vacuum deposition on the surface of the light-emitting layer 6B, forming the cathode 8.

Finally, to form a sealing layer 9. Instead of providing the sealing layer 9, in the case of using a sealing can, sealing can for example be made of the same material as the substrate 1, provided with a getter for adsorbing moisture such as in a closed space.

Through the above steps, the organic EL element 1000 is completed.

<Discussion and various experiments on the conditions for forming the hole injection layer 4>
(For conditions for forming the hole injection layer 4)
In the present embodiment, by forming the tungsten oxide constituting the hole injection layer 4 at a predetermined deposition conditions, to improve the hole conductivity by the presence of nanocrystals structural intentionally hole injection layer 4 , and to allow low voltage driving organic EL element 1000. This predetermined deposition conditions will be described in detail.

Using a DC magnetron sputtering apparatus as a sputtering apparatus, the target was a metallic tungsten. Control of the substrate temperature was not carried out. Sputtering gas composed of argon gas, the reactive gas is composed of oxygen gas is believed that it is preferable to deposition under the conditions using a reactive sputtering method using each of the gas with an equivalent flow rate. Note that it forming method of the hole injection layer 4 is not limited thereto, a method other than sputtering, such as vapor deposition, also be formed by a known method such as CVD.

To form a highly crystalline tungsten oxide layer, atoms must form a film with regularity is formed on the substrate, it is desirable that the film formation at a low deposition rate as possible.
Here, the deposition rate in the sputtering, will depend on the condition of the above (1) to (4). Then, as a result of experiments described below, (1) if - (4) takes a numerical range of the driving voltage has been confirmed to be reduced by this, highly crystalline tungsten oxide layer so that has been obtained.

Note that relates to the aforementioned (1), in the experimental conditions described later, although the total pressure of the sputtering gas the upper limit is 4.7Pa, at least until 7.0Pa to show similar tendency separately has been confirmed also it relates to the aforementioned (2), the ratio of oxygen gas partial pressure is set to 50% of the sputtering gas total pressure, at 70% or less at least 50% or more, reduction of the driving voltage has been confirmed.

Furthermore, it relates to the aforementioned (4), supplementary explanation. When the flow rate ratio of argon gas and oxygen gas is equal, it seems to determine the input power density and deposition time pressure (total pressure). Input power density of the (3) varies the number and energy of the tungsten atoms or tungsten atom clusters are sputtered. That is, by lowering the input power density, the number of tungsten sputtered is reduced, the tungsten is deposited on the substrate can be deposited at low energy can be expected film of at TeiNarumaku rate. Total pressure during film deposition of (1), the tungsten atoms or tungsten atom clusters emitted to be sputtered in the gas phase is to change the mean free path until arriving at the deposition substrate. That is, the total pressure is high, the probability that the tungsten atom or tungsten atom clusters repeated collisions with the gas component of the film forming chamber until arriving at the substrate is increased, the randomness of the tungsten atoms or tungsten atom clusters are flying by increases, reduces the number of tungsten that is deposited on the substrate, it is believed that tungsten can be deposited at low energy. Thereby expected film of low-deposition rate.

However, the input power density to vary the deposition rate of the sputtering is believed that there is a limit to increase the controlled device characteristics the total pressure during the deposition singly. Therefore, the total pressure during film formation (Pa) / input power density (W / cm 2), which was defined as a new film formation conditions (4), was used as an index for determining the deposition rate of the tungsten atoms.

As the film formation conditions (4) is high, it becomes low driving voltage, low deposition rate, while the deposition parameter (4) the lower, higher driving voltage, the deposition rate tends to be high it has been experimentally confirmed is.

Specifically, as the total pressure / power density below experimental conditions, it is 0.78Pa · cm 2 / W or more, considered necessary to be greater than 0.7 Pa · cm 2 / W, more certainly, it may be preferably 0.8Pa · cm 2 / W or more. On the other hand, the upper limit of the total pressure / power density, on the experimental conditions, not more than 3.13Pa · cm 2 / W, believed to be smaller than 3.2 Pa · cm 2 / W, the more reliable the it is believed that it is preferably not more than 3.1Pa · cm 2 / W, as described above, from the viewpoint of film formation rate, is always considered the upper limit is not restricted.

It was then carried out various experiments to confirm the validity of the above-mentioned film-forming conditions.

First, the hole conduction efficiency from the hole injection layer 4 to the buffer layer 6A, order to evaluate the deposition condition dependent, to produce a hole-only device 1000A shown in FIG. 2 as an evaluation device.

In the organic EL device that actually operates, the carrier to form a current is both holes and electrons. Therefore, the electrical characteristics of the organic EL element, the electron current is also reflected in the other hole current. However, since the Hall-only device is inhibited injection of electrons from the cathode, the electron current hardly flows, the total current becomes to be composed of only approximately Hall current. That is, the carrier can be regarded only as holes, hole-only device is suitable for evaluation of hole conduction efficiency.

As shown in FIG. 2, a hole-only device 1000A is obtained by replacing the cathode 8 in the organic EL element 1000 in FIG. 1, the cathode 8A made of gold. Specifically, prepared in accordance with the manufacturing method described above, the thickness of each layer, 70 nm light-emitting layer 6B made a buffer layer 6A made of the hole injection layer 4 made of tungsten oxide 30 nm, from the TFB 20 nm, from F8BT, the cathode 8A made of gold was 100nm.

In the manufacturing process of the Hall-only device 1000A, the hole injection layer 4, using a DC magnetron sputtering apparatus was deposited by reactive sputtering. Chamber gas is composed of at least one of argon gas and oxygen gas, the target using a metal tungsten. The substrate temperature was not controlled, the total pressure was assumed to be regulated by the flow rate of each gas. As shown in Table 1, to prepare a hole-only device 1000A in five conditions for forming the A ~ E. As shown in Table 1, the respective film forming conditions, varying total pressure and input power density. The partial pressure of argon gas and oxygen gas in the chamber is 50%, respectively.

Hereinafter, the formed hole-only devices 1000A to HOD-A in the film formation conditions A, the formed hole-only devices 1000A to HOD-B in the film forming conditions B, and Hall-only device 1000A is formed in the deposition condition C HOD -C, Hall-only elements 1000A to HOD-D is formed in the deposition condition D, and Hall-only device 1000A is formed in the deposition condition E referred HOD-E.

Each hall-only element fabricated connected to the DC power supply DC, a voltage was applied. Changing the applied voltage at this time was converted into a value (current density) per unit area of ​​the element value of the current that flowed in accordance with the voltage value.

Figure 3 is a device characteristic diagram showing the relationship curve between the applied voltage and the current density of each hole-only devices. The vertical axis in the drawing current density (mA / cm 2), the horizontal axis is the applied voltage (V).

Table 2 shows the value of the driving voltage of each sample HOD-A ~ HOD-E obtained by the experiment. Table 2 in the "drive voltage" is the voltage applied at a current density of 0.3 mA / cm 2 a practical specific value.

As this driving voltage is small, hole conduction efficiency of the hole injection layer 4 can be said to be high. This is because, in each hole-only devices, since the manufacturing method of each part other than the hole injection layer 4 are identical, except for the hole injection layer 4, a hole injection barrier between the adjacent two layers are considered constant. Further, ITO layer 3 and the hole injection layer 4 used in the experiment, it has an ohmic connection, it was confirmed in a separate experiment. Therefore, the difference in driving voltage due to the deposition conditions of the hole injection layer 4 can be said to be a reflection strongly hole conduction efficiency from the hole injection layer 4 to the buffer layer 6A.

Table 2, as shown in FIG. 3, HOD-A ~ HOD-E is the input power density with decreasing the total pressure during film formation in comparison with HOD-E prepared in conditions to maximize hole conductive it can be seen that the efficiency is excellent.

Having described the verification of hole conduction efficiency of the hole injection layer 4 in the Hall-only elements 1000A, Hall-only element 1000A is the same configuration as the organic EL element 1000 which actually operates (FIG. 1) except the cathode 8A . Therefore, in the organic EL element 1000, film-forming condition dependency of the hole conduction efficiency from the hole injection layer 4 to the buffer layer 6A is essentially the same as the Hall-only element 1000A. To confirm this, to produce an organic EL element 1000 using the hole injection layer 4 formed under the film formation conditions A ~ E. Hereinafter, the formed organic EL element 1000 BPD-A in the film formation conditions A, BPD-B organic EL element 1000 is formed in the deposition condition B, and the organic EL element 1000 is formed in the deposition condition C BPD -C, BPD-D organic EL element 1000 is formed in the deposition condition D, and the organic EL element 1000 is formed in the deposition condition E is referred to as BPD-E.

Each organic EL device produced were created based on the above-described manufacturing method. The thickness of each layer becomes 30nm hole injection layer 4 made of tungsten oxide, 20 nm buffer layer 6A made of TFB, 70 nm light-emitting layer 6B made of F8BT, an electron injection layer 7 made of barium layer 5 nm, an aluminum layer the cathode 8 was set to 100nm. Each organic EL element 1000 of the deposition condition A ~ E produced connected to the DC power supply DC, a voltage was applied. Changing the applied voltage at this time was converted into a value (current density) per unit area of ​​the element value of the current that flowed in accordance with the voltage value.

Figure 4 is a device characteristic diagram showing the relationship curve between the applied voltage and the current density of each organic EL element. The vertical axis in the drawing current density (mA / cm 2), the horizontal axis is the applied voltage (V). Table 3 shows the values ​​of each sample the drive voltage of the resulting BOD-A ~ BOD-E by the experiment. The "drive voltage" in Table 3, the applied voltage at a current density of 8 mA / cm 2 a practical specific value.

Table 3, as shown in FIG. 4, BPD-E, compared with other organic EL elements, the most current density - the rise of the applied voltage curve is slow, in order to obtain a high current density is the highest applied voltage it was confirmed that. This is a Hall-only device similar tendency to HOD-A ~ HOD-E of the same film-forming conditions, respectively.

From the above results, the deposition conditions dependency of hole conduction efficiency of the hole injection layer 4 is, in the organic EL element 1000, it was confirmed that acts as in the Hall-only element 1000A. That is, the film formation conditions A, B, C, by performing film formation in the deposition conditions in the range and D, to improve hole conduction efficiency from the hole injection layer 4 to the buffer layer 6A, whereby low voltage drive but it was confirmed to be realized.

In the above, conditions of input power, expressed in input power density as shown in Table 1. When using different DC magnetron sputtering apparatus with a DC magnetron sputtering apparatus used in this experiment, in accordance with the size of the target rear surface of the magnet, by input power density to adjust the input power so that the above conditions, the Like the experiment, it is possible to obtain a hole injection layer 4 of good tungsten oxide layer of hole conduction efficiency. Incidentally, the total pressure, the partial pressure of oxygen, and devices target size and does not depend on the target magnet size.

Moreover, during film formation by reactive sputtering of the hole injection layer 4 is, in the sputtering apparatus are placed in the room temperature, is intentionally the substrate temperature is not set. Accordingly, the substrate temperature before at least the deposition was room temperature. However, the substrate temperature during the film formation could rise several 10 ° C..

Incidentally, the present inventors another experiment, in the case where too high an oxygen partial pressure has been confirmed that the reverse to the drive voltage is increased. Therefore, the oxygen partial pressure is preferably 50% to 70%.

From the above experimental results, the film formation conditions for low voltage drive A, B, C, the organic EL device preferably comprises a hole injection layer prepared in D, the organic EL devices fabricated more preferably the film formation conditions A, in B it is. Hereinafter, the deposition conditions A, B, C, the organic EL element including a hole injection layer prepared in D and application of interest.

(For chemical state of the tungsten in the hole injection layer 4)
Tungsten oxide constituting the hole injection layer 4 of the organic EL element 1000 of this embodiment, the nanocrystal structure exists as described above. The nanocrystal structure is intended to be formed by adjusting the film forming conditions shown in the previous experiments. Described in detail below.

In the tungsten oxide is deposited in the deposition condition A ~ E of the above, in order to confirm the presence of nanocrystals structure, hard X-ray photoelectron spectroscopy (HAXPES) measurement (hereinafter, simply referred to as "XPS measurement".) Experiment It was carried out. Here, generally hard X-ray photoelectron spectroscopy (hereinafter, simply referred to as "XPS spectrum".) Has a surface of the measuring object, the angle formed by the direction detecting photoelectrons in the detector taking out photoelectrons, film information depth that reflects the average valence is determined. Therefore, in this experiment, the photoelectron detection direction in the XPS measurement, and that the angle of the surface of the tungsten oxide layer was measured under the condition that the 40 °, observing the average valence state of the thickness direction of the tungsten oxide layer did.

XPS measurement conditions are as follows. It should be noted that, during the measurement, the charge-up did not occur.

(XPS measurement conditions)
Equipment used: R-4000 (VG-SCIENTA Co., Ltd.)
Light source: synchrotron radiation (7856eV)
Bias: no emission angle: angle between the substrate surface 40 °
Measurement point interval: 0.05eV
Samples were prepared for XPS measurement by each film formation conditions A ~ E shown in Table 1. On the ITO conductive substrate which is formed on glass, the hole injection layer 4 having a thickness of 30 nm, by depositing by reactive sputtering described above, was used as a sample for XPS measurement. Thereafter, film formation conditions A, B, C, D, a sample for XPS measurement was produced in E, referred respectively Sample A, Sample B, Sample C, Sample D, and Sample E. Subsequently, XPS measurement was performed for each hole injection layer 4 on the surface of the sample A ~ E. The resulting spectrum is shown in FIG.

The horizontal axis of FIG. 5 shows the binding energy corresponds to the photoelectron energy present in each level position when relative to the X-ray, was left as a positive direction. The vertical axis shows the photoelectron intensity, corresponding to the observed number of photoelectrons. Observed three peaks as shown in FIG. 5, each peak from left to right in the figure, respectively 5p 3/2 level position tungsten (W5p 3/2), 4f 5/2 level position (W4f 5 / 2), it was assigned to be the peak corresponding to the 4f 7/2 level position (W4f 7/2).

Next, W5p 3/2 of the spectrum of sample E as a comparative example with the spectrum of sample A, W4f 5/2, to peaks attributed to W4f 7/2, were peak fitting analysis.
Peak fitting analysis was carried out in the following manner.

Specifically, it was performed using photoelectron spectroscopic analysis software "XPSpeak Version4.1". First, the photoionization cross section of 7940eV energy of the hard X-rays, W4f 7/2 quasi position, W4f 5/2 quasi position, the ratio of the integrated intensity of a peak corresponding to W5p 3/2 level, W4f 7/2 : W4f 5/2: W5p 3/2 = 4 : 3: fixed with 10.5, as shown in Table 4, the hexavalent surface defect level of W4f 7/2 (W 6+ 4f 7/2) the sum of the peak top, which is attributed to the energy value of 35.7eV. Next, the surface photoelectron peak of W5p 3/2 (W sur 5p 3/2) , 6 -valent surface defect level (W 6+ 5p 3/2), 5-valent surface defect level (W 5+ 5p 3/2 the peak energy value and a peak half-width of each attribution peak attributed to), were set to the values ​​shown in Table 4. Similarly, W4f 5/2, even for W4f 7/2, surface photoelectron peak (W sur 4f 5/2, W sur 4f 7/2), 6 -valent surface defect level (W 6+ 4f 5/2 ), pentavalent surface defect level (W 5+ 4f 5/2, the value of the peak energy value and a peak half-width of each attribution peak attributed to W 5+ 4f 7/2), set as shown in Table 4 did. After setting the peak intensity in an arbitrary intensity, by calculating up to 100 times with a mixed function of the Gaussian-Lorentzian, to give a final peak fitting analysis results. The ratio of the Lorentzian function in the mixed function is shown in Table 4.

The final peak fitting analysis results shown in FIG. 6 (a) is the analysis result of the sample A, FIG. 6 (b) is a result of analysis of sample E.

In both figures, a broken line (sample A, sample E) is measured spectrum (corresponding to the spectrum of FIG. 5), the two-dot chain line (Surface) surface photoelectron peak W sur 5p 3/2, W sur 4f 5/2, W sur spectra attributed to 4f 7/2, dashed line (W 6+) hexavalent surface defect level W 6+ 5p 3/2, W 6+ 4f 7/2, attributed to (W 6+ 4f 5/2) it is the spectrum, the dashed line (W 5+) pentavalent surface defect level W 5+ 5p 3/2, W 5+ 4f 5/2, a spectrum attributed to W 5+ 4f 7/2. The solid line (fit) is a spectrum obtained by adding the spectrum shown by the two-dot chain line and the dotted line and dashed line. Note that in both figures, a peak attributed to pentavalent tungsten indicated by a dashed line, was considered to be due only to the pentavalent state tungsten.

As shown in each of FIGS. 6, 5p 3/2, 4f 5/2, the spectrum attributed to the quasi-position of 4f 7/2 is the peak (Surface) by photoelectrons from the surface of the hole injection layer 4 , the hole injection layer 4 in layer by hexavalent tungsten contained in the depth of photoelectrons are detected peak and (W 6+), plus the peak of pentavalent tungsten contained in the depth (W 5+) alignment it can be seen which is constituted by.

Further, as shown in FIG. 6 (a), in the sample A, 5p 3/2 in the spectrum of the W 6+, 4f 5/2, from a peak attributed to the quasi-position of 4f 7/2, 0.3 in ~ 1.8 eV lower binding energy region, it is seen that the peak of W 5+ corresponding to each level is present. On the other hand, as shown in FIG. 6 (b), the sample E, not could see the peaks of such W 5+. For clarity, the right side of FIG. 6 (a) and 6 (b), showing an enlarged view of a peak attributed to 4f 7/2 in the spectrum of the W 5+ of Samples A and E. As shown in the same figure (c), but it can be confirmed that the peak of the sample A in clearly W 5+ is present, the peak of the sample E W 5+ is not found.

Further, paying attention to the details of the enlarged view of FIG. 6, the spectrum of alignment sum of the peak fit Tin indicated by the Sample A solid line (fit), significantly between the spectrum of W 6+ indicated by the dotted line (W 6+) while there is a "deviation", "deviation" of about the sample E sample a is not. That is, the in sample A "shift" is presumed that suggest the presence of pentavalent tungsten.

Next, in the sample A ~ E, it was calculated and the presence ratio of the number of elements of the pentavalent tungsten W 5+ / W 6+ for element number of hexavalent tungsten. The existence ratio is, the area intensity of the peak of W 5+ (dashed line) in the spectrum obtained by peak fitting analysis of each sample was calculated by dividing the integrated intensity of the peak of W 6+ (dotted line).

Incidentally, in principle, by the ratio of area intensity of the peak area intensity and W 5+ peak W 6+ in W4f 7/2, represent a number abundance ratio of the number and pentavalent tungsten atoms hexavalent tungsten atoms is synonymous with representing the existence ratio of a peak attributed to W5p 3/2 and W4f 5/2. Indeed, it the present study, the ratio of the integrated intensity of the integrated intensity and W 6+ 4f 7/2 of W 5+ 4f 7/2 in W4f 7/2 is the same value even if W5p, the W4f 5/2 it has been confirmed. Therefore, in the following discussion, it was decided to examine using only peak attributed to W4f 7/2.

Table 5 shows the W 5+ / W 6+ of sample A ~ E.

Than the value of W 5+ / W 6+ shown in Table 5, a most pentavalent Sample A Included tungsten atom, followed by the sample B, sample C, and that the ratio is less in the order of Sample D confirmed. Further, from the results in Table 3 and Table 5, as the value of W 5+ / W 6+ is large, the driving voltage of the organic EL device was found to be lower.

(Electronic state of the tungsten in the hole injection layer 4)
The tungsten oxide was deposited at the aforementioned film formation conditions A ~ D, in its electronic state, the upper end of the valence band, i.e. than the lowest binding energy valence band, 1.8 ~ 3.6 eV lower binding energy occupancy levels are present in the region. The occupancy level is corresponds to the highest occupied level of the hole injection layer 4, i.e., the binding energy range closest to the Fermi surface of the hole injection layer 4. And later, the occupancy level is referred to as "occupied level near the Fermi surface."

By occupying level of the Fermi surface vicinity is present, in the lamination interface between the hole injection layer 4 and the buffer layer 6A, a so-called interface state connection is made, the binding energy of the highest occupied molecular orbital of the buffer layer 6A is Hall and binding energy of the occupied level of the Fermi surface near the injection layer 4 is approximately equal. That is, by this occupation levels are present, it is possible to reduce the hole injection barrier between the hole injection layer 4 and the buffer layer 6A. As a result, it is possible to obtain better hole conduction efficiency, it is possible to drive at a low voltage.

Here, the "substantially equal" and "interface state connection is made" in the interface between the hole injection layer 4 and the buffer layer 6A, and the lowest binding energy occupancy levels near the Fermi surface, the difference between the lowest binding energy at the highest occupied molecular orbital, which means that the range within ± 0.3 eV.

Further, herein, the term "interface" refers to the surface of the hole injection layer 4, a region including a buffer layer 6A in the distance within 0.3nm from the surface.

Moreover, occupancy level of the Fermi surface vicinity is desirably present throughout the hole injection layer 4, may be present at the interface between at least the buffer layer 6A.

Next, with respect to the hole injection layer 4 described above in Sample A and Sample E, an experiment to confirm the presence of occupancy levels near the Fermi surface, it was performed using an ultraviolet photoelectron spectroscopy (UPS) measurement.

Both samples A, E, after forming the hole injection layer 4 in the sputtering apparatus, and transferred to the sputtering apparatus glove box a nitrogen gas is connected is filled in, keeping the state in which no air exposure. Then, sealed into a transfer vessel in the glovebox, and attached to the photoelectron spectrometer. Thus, without exposure to the atmosphere hole injection layer 4 after film formation was performed UPS measurement.

Here, generally UPS spectra definitive up to several nm depth from the surface of the measuring object, the reflect the state of occupancy levels, such as the valence band. Therefore, in this experiment it was intended to observe the state of occupancy levels in the surface layer of the hole injection layer 4 by using the UPS measurement.

UPS measurement conditions are as follows. It should be noted that, measured in the charge-up did not occur.

(UPS measurement conditions)
Using equipment: scanning X-ray photoelectron spectrometer PHI5000 VersaProbe (manufactured by ULVAC-PHI, Inc.)
Light source: the He I line bias: None emission angle: substrate normal direction measuring point interval: 0.05 eV
Figure 7 shows a UPS spectrum of the hole injection layer 4 surface in the sample A. The origin of the binding energy of the horizontal axis is the Fermi surface of the substrate 1, and the leftward direction as a positive direction. Hereinafter, with reference to FIG. 7, a description will be given of each occupancy level of the hole injection layer 4.

[Correction under Rule 91 14.09.2010]
In general UPS spectrum indicated tungsten oxide, largest steep rise is uniquely determined. The tangent through the inflection point of the rising line (i), the intersection of the horizontal axis and the point (iii). Thus, UPS spectrum of tungsten oxide, a region located in the high binding energy side from the point (iii) (x), is divided into a region located low binding energy side (i.e. the Fermi surface side) (y).

Here, using the same XPS measurements above, sample A, with E, approximately the ratio of the number of tungsten atoms and oxygen atoms was 1: Verify that is 3. Specifically, it was carried out by estimating the proportion of tungsten and oxygen in to several nm depth from the surface of the hole injection layer 4.

[Correction under Rule 91 14.09.2010]
From this ratio, Samples Sample A, in any of E, in the range of few depth nm from at least the surface hole injection layer 4, (described in detail below) the atomic arrangement of the basic tungsten trioxide basic structure It is considered to have to. Accordingly, regions in FIG. 7 (x) is the occupancy level derived from the basic structure is a region corresponding to a so-called valence band. Incidentally, the present inventors have carried out an X-ray absorption fine structure (XAFS) measurements of the hole injection layer 4, sample A, in any of E, it was confirmed that the basic structure is formed.

[Correction under Rule 91 14.09.2010]
Therefore, the region (y) in FIG. 7 is corresponding to the band gap between the valence band and the conduction band, as indicated by the UPS spectrum, the tungsten oxide in the region, different from the valence band it is known that the occupancy levels may be present. This is a level derived from another structure that is different from the above-mentioned basic structure, the so-called inter-band gap level (in-gap
state or a gap state).

[Correction under Rule 91 14.09.2010]
8 Subsequently, the sample A, the respective hole injection layer 4 in the E, shows the UPS spectrum in the region (y). Intensity of the spectrum shown in FIG. 8, normalized by the value of the peak top of a peak (ii) is located in the high binding energy side as 3 ~ 4 eV than the point (iii) in FIG. It indicates the point (iii) on the same horizontal axis position and the point of FIG. 7 (iii) in FIG. 8. The horizontal axis relative value relative to the point (iii) expressed as (relative binding energy) bonding energy to the right (the Fermi surface side) from the left shows to be lower.

As shown in FIG. 8, the region of the hole injection layer 4 of the sample A, from approximately 3.6eV position of low binding energy from the point (iii), to the position of approximately 1.8eV lower binding energy from the point (iii) , the presence of the peak can be confirmed. A clear rising position of the peak indicated at point (iv) in FIG. Such a peak is, can not be confirmed in the sample E.

Thus, the tungsten oxide having a structure that protrudes from the point (iii) in the UPS spectrum 1.8 ~ 3.6 eV lower by about binding energy in the region (not necessarily the peak), by using as a hole injection layer , excellent hole conduction efficiency in the organic EL device has to be exerted.

Here, as the degree of the ridge is sharp, it has been found that the hole injection efficiency is high. Accordingly, as shown in FIG. 8, the region of 2.0 ~ 3.2 eV lower by about binding energy from the point (iii) it is easy to confirm the relatively the ridge structure, and the ridge is relatively steep region as, it can be said to be of particular importance.

(Relationship between the value and the drive voltage of W 5+ / W 6+)
Figure 9 is a diagram for explaining the structure of the tungsten oxide layer. Here it will be described as an example tungsten trioxide (WO 3) as tungsten oxide. As shown in FIG. 9, a single crystal of tungsten oxide has a rutile structure in which oxygen atom is bonded in octahedral coordination with respect to tungsten atoms in the basic structure. In FIG. 9, is shown in rutile structure trioxide tungsten single crystal for simplicity, it is actually distorted rutile structure.

As shown in FIG. 9, the tungsten atoms in the crystal interior has been terminated with an oxygen atom, a tungsten atom in the crystal grain boundaries that are not terminated surrounded therewith terminating oxygen atom (b) (a) is present Conceivable. Non-Patent Document 4, the first-principles calculation, than all of the tungsten atoms in the crystal grain boundary is terminated by an oxygen atom, periodically a part of the tungsten atoms as shown in FIG. 9 (a) is not terminated structure disclosed energetically stable found the following. The reason for this electrical repulsion of all the tungsten atoms to each other terminated by the terminating oxygen atom by an oxygen atom in the crystal grain boundary is increased, have reported is because the rather unstable. That is, in the grain boundaries, Write structure similar to oxygen defects on the surface (a) is to stabilize.

Here, tungsten atoms are terminated with oxygen atom, i.e., having no tungsten atoms the structure (a) similar to the oxygen defects corresponds to the hexavalent tungsten atoms. On the other hand, tungsten atoms are not terminated with oxygen atoms, i.e., tungsten atoms having the structure (a) similar to the oxygen defects corresponds to the pentavalent tungsten atoms (including less than 5 or more hydroxyl hexavalent).

Pentavalent tungsten atoms are believed to have a structure having an unshared electron pair by not spliced ​​1 of oxygen atoms octahedral coordination. In other words, pentavalent tungsten atoms will donate an unshared electron pair with itself in the hole, whereby pentavalent tungsten atom donating the electrons is considered will have a hole. By the bias voltage applied to the hole injection layer, a donor lone pair that exists pentavalent tungsten atoms are continuously caused it, Hall potential lower direction, the electrons move to a higher potential direction, the hole conductive It is considered to occur. Therefore, the value of W 5+ / W 6+ as sample A is high, i.e., a number pentavalent tungsten atoms hole injection layer 4, the hole conductive path is high proportion of low-voltage drive by the Hall conductivity at low voltage There realized, excellent hole conduction efficiency in the organic EL device has to be exerted as a result.

Also, sample C, and the D, the value of W 5+ / W 6+ is but not as high as the sample A, it was also confirmed that even in the order of 3.2% has good hole conducting occurs.

(Fine Structure of tungsten in the hole injection layer 4)
The tungsten oxide layer constituting the hole injection layer 4, the nanocrystal structure is present. The nanocrystal structure is intended to be formed by adjusting the film formation conditions. Described in detail below.

Film formation conditions shown in Table 1 A, B, C, D, in the formed tungsten oxide layer by E, in order to confirm the presence of nanocrystals structure was a transmission electron microscope (TEM) observation experiments.

Tungsten oxide layer in the sample for TEM observation, using a DC magnetron sputtering device under the conditions shown in Table 1 was deposited by reactive sputtering. The structure of the sample, on the ITO conductive substrate which is formed on glass, the hole injection layer 4 having a thickness of 30nm was deposited by reactive sputtering of the. Thereafter, film formation conditions A, B, C, D, the TEM observation sample manufactured in E, referred respectively Sample A, Sample B, Sample C, Sample D, and Sample E. Incidentally, TEM observation, by the previous XPS measurement, samples A, B, C, is carried out after confirming that it contains the pentavalent tungsten atoms in D.

Here, generally TEM observation, performing the thickness flaked observed for observation surface. Flakes of the present embodiment, the depth direction of the thickness of the cross section in the tungsten oxide layer, and the sample processed with a focused ion beam (FIB) apparatus, and a thin of about 100 nm. Conditions of FIB processing and TEM observation are as follows.

(FIB processing conditions)
Used equipment: Quanta200 (FEI Co., Ltd.)
Acceleration voltage: 30kV (final finishing 5kV)
Slice thickness: ~ 50nm
(TEM observation conditions)
Used equipment: Topcon EM-002B (Topcon Techno house Co., Ltd.)
Observation method: High-resolution electron microscopy accelerating voltage: 200 kV
Figure 10 shows sample A, B, C, D, a TEM observation photograph of the hole injection layer 4 cross-section of the E. Scale photographs in accordance with the scale bar described in the photograph, the display size of the TEM photograph is displayed in 560 × 560 pixels. Furthermore, TEM observation photograph shown in Figure 10 is displayed on average divided into 256 gradations from black dark portion to the twilight unit.

From TEM photograph shown in FIG. 10, samples A, B, C, by partially bright portion are arranged in the same direction in the D, regularly arranged linear structure is confirmed. The linear structure is, from the scale in the TEM photograph was found to be arranged at intervals of approximately 1.85 ~ 5.55Å.

On the other hand, the linear structure bright portion is irregularly distributed, regularly arranged in sample E was not confirmed. In the TEM photograph, the regions where there is a linear structure of the above represents one of the nanocrystals tungsten oxide, from TEM photographs, samples A, B, C, formation of the nanocrystal structure D in the tungsten oxide is confirmed It was. On the other hand, the formation of the nanocrystal structure in the sample E was not confirmed.

In the TEM photograph of Sample A in FIG. 10, the illustrated any one of the nanocrystals in the white line frame. Incidentally, the contour is not correct, it is only illustrative. Since, in fact, In the photo TEM photograph not only the outermost surface, since the crowded also-through the underlying situation, because it is difficult to determine the exact contour. The size of one nanocrystals are shown in white line frame in the sample A is approximately about 3 ~ 10 nm.

Figure 11 shows the results of two-dimensional Fourier transform of the TEM observation photograph shown in FIG. 10 as 2-dimensional Fourier transform image. 2-dimensional Fourier transform image shown in FIG. 11 is a distribution showing the reciprocal space of the TEM observation photograph shown in FIG. 10. Specifically, two-dimensional Fourier transform image shown in FIG. 11, using "LAview Version # 1.77" image processing software the TEM photograph shown in FIG. 10 were Fourier transform. Fourier change image shown in FIG. 11, sample A, B, C, 3 present or two concentric bright portion around the center point of the Fourier transform image at D is confirmed. Further, samples A, B, C, concentric bright portion of the Fourier transform image is confirmed by D can be confirmed to have an indistinct circle in Sample E. This "obscurity" concentric bright portion shows qualitatively collapse of orderliness of structure in the hole injection layer 4 shown in FIG. 10. In other words, it shows that sample A circular bright portions can be clearly confirmed, B, C, In D, has high orderliness, the orderliness Sample E is collapsed.

Then, from the two-dimensional Fourier transform image shown in FIG. 11, to create a graph showing a change in luminance with respect to the distance toward the outer periphery from the center point of the image. Figure 12 is a diagram showing an overview of the creation method, a sample A as an example.

As shown in FIG. 12 (a), by rotating one by 1 ° as the axis of the center point of the Fourier transform image, measuring the luminance with respect to distance from the center point of the Fourier transform image to photograph the outer peripheral portion of the X-axis direction. 0 to 359 ° rotated from ° distance from the center point of the Fourier transform image during rotation in increments of each 1 ° (horizontal axis), a value obtained by normalizing the luminance of the Fourier transform image normalized luminance (vertical axis) integrated, and by dividing by 360, drawing the graph shown in Figure 12 (b). Note that the rotation of the image, using "Microsoft Office Picture Manager", the measurement of distance and luminance from the center of the Fourier transform image, using the image processing software "ImageNos". Hereinafter, a plot drawn based on the technique described in Figure 12 is referred to as a "luminance change Plot".

13 and 14 shows a sample A, B, C, D, the luminance variation plot for E. Samples A, B, C, D, the luminance variation plots in E, it is found to have a peak indicating separately by P1 and the high-luminance portion of the center points in each sample. Hereinafter, the peak of the normalized luminance appearing closest to the central point in the luminance variation plot referred to as "peak P1". Further, as compared with the peak P1 in the sample E, the sample A, B, C, and the peak P1 is to have a sharp convex shape in D was confirmed.

Next, samples A, were evaluated B, C, D, the sharpness of the peak P1 in E. Figure 15 is a diagram showing an outline of the evaluation method, the sample A and sample E is shown as an example.

Figure 15 (a), (b), respectively, the luminance variation plot of Sample A and Sample E, FIG. 15 (a1), (b1) is an enlarged view of the vicinity of the peak P1 of each sample. Figure 15 (a1), will be used as an indicator of the "peak width L of the peak P1", "sharpness" of the peaks P1 shown by L in (b1).

In order to determine the "peak width L of the peak P1 'more accurately, Figure 15 (a1), and first derivative plots indicated by (b1), Figure 15 it (a2), as shown in (b2). In FIG. 15 (a2), (b2), the value of the horizontal axis corresponding to the peak top of the peak P1, the value of the horizontal axis corresponding to a position at which the differential intensity is 0 in the beginning toward the center point of the peak top the difference between the peak width L. When normalized as 100 the value of the horizontal axis corresponding to the center point and the peak top of the peak P1 of the Fourier transform image, samples A, B, C, D, the value of peak width L in E shown in Table 6.

As shown in Table 6, Sample A most peak width L is small, samples B, C, peak width L is increased in the order and D, the peak width L of sample E was confirmed that the maximum. Also, sample C, and the D, the value of peak width L is small not enough sample A, it was also confirmed that even in the order of 21.9 has occurred good hole conducting.

The value of peak width L shown in Table 6 shows the clarity of the nearest concentric bright portion from the center value of the Fourier transform image shown in FIG. 11, as the value of peak width L is small, concentric JoAkira portion less spread, that is, the higher regularity in TEM photograph of the hole injection layer 4 shown in FIG. 10. Conversely, as the value of peak width L is large, it indicates that the bright portion closest concentrically from the center of the Fourier transform image shown in FIG. 11 has a spread, i.e., the holes shown in Figure 10 regularity of the microstructure in the TEM photograph of the injection layer 4 indicates that collapsed.

As described in FIG. 9, a single crystal of tungsten oxide, an oxygen atom is octahedral coordination to tungsten atoms, it is believed to have a rutile structure distorted the basic structure. Also, nanocrystals structure, such a single crystal, i.e. one in which the nanocrystals are constituted by a set number. In other words, the interior of the nanocrystal structure is also distorted rutile structure and the inside of the single crystal is considered to be a highly ordered structure. Thus, pentavalent tungsten atoms are not within the nanocrystal, it should be considered to be present on the surface between the nanocrystals.

Table 5, from the results of Table 6, as the tungsten oxide layer is low film structure regularity, the ratio of the pentavalent tungsten atom was found to be lowered. The reason for this is considered as follows.

Tungsten oxide layer produced in the film formation conditions E is rutile structure described above is present with orderliness in some, the most in the film, an amorphous structure in which a rutile structure has no orderliness It is considered to have become. In the portion that an amorphous structure, although the rutile structure has no orderliness, rutile structure has a connection in the entire film, less break portions are cutting an array of rutile structure. Therefore, grain boundary oxygen defects there are many less, as a result, the ratio of the pentavalent tungsten atoms decreases. Therefore, fewer parts to be hole conduction path, while it is believed that low-voltage driving is hard realized, in the tungsten oxide layer produced in the film formation conditions A ~ D, the rutile structure with orderliness throughout film are present Te. Portion having its orderliness is considered to be originated from the nanocrystals. In the portion where nanocrystals are present, although the rutile structure has a orderliness, there are many discontinuities portion of the rutile structure. The break portion is equivalent to the crystal grain boundaries of the nanocrystals. Lack of oxygen in the grain boundaries, i.e. oxygen defects occur, the greater the amount of pentavalent tungsten atoms accordingly. As a result, increased site a hole conducting path is believed that low-voltage driving can be realized.

(Study hole conduction of injected holes)
As described above, a single crystal of tungsten oxide is oxygen atom bonded in octahedral coordination with respect to tungsten atoms, believed to rutile structure distorted the basic structure. If this rutile structure has formed into a film without a orderliness becomes amorphous structure, when the rutile structure was formed into a film with orderliness is believed that the nanocrystal structure.

If the tungsten oxide layer is pentavalent tungsten atoms are present, by not spliced ​​1 octahedral coordination to have an oxygen atom with respect to tungsten atoms, tungsten atoms are a structure having an unshared electron pair I think that the. In other words, pentavalent tungsten atoms will donate an unshared electron pair with its own tungsten atom having a hole, pentavalent tungsten atom donating an unshared pair of electrons is considered will have a hole. By the bias voltage applied to the hole injection layer, a donor lone pair that exists pentavalent tungsten atoms are continuously caused it, Hall potential lower direction, the electrons move to a higher potential direction, the hole conductive It is considered to occur. Thus, pentavalent tungsten atoms as contained many, will exist many contributing tungsten atoms in hole conduction, hole conduction efficiency is improved. However, it contains many pentavalent tungsten atom, not a necessary and sufficient condition hole conductivity improves. The reason will be described with reference to FIG. 16.

16 (b) is a conceptual diagram of a state in which the hole 14 is conducted by hopping conduction is a diagram showing a conduction hole 14 in the case of amorphous structure. The amorphous structure, in the figure, the part indicated by 11 is a portion of the crystalline rutile structure has a orderliness (segregated crystal 15), the surface of the segregated crystal 15 there are many pentavalent tungsten atoms . On the other hand, rutile structure does not have a orderliness in a region 16 other than the segregated crystal 15, and an amorphous portion, pentavalent tungsten atoms are not so much as the surface of the segregated crystal 15 exists. In amorphous structure, although segregated pentavalent tungsten atoms on the surface of the crystal 15 are present, while the other pentavalent tungsten atoms close to the pentavalent tungsten atoms because there is no overlap of orbitals of each tungsten atom , the hole 14 between each of the pentavalent tungsten atoms hall by hopping seems to conduction. That is, when the amorphous structure, a long distance between the pentavalent tungsten atom, the transfer of holes between pentavalent tungsten atoms that can be the hole conductive portions, is necessary to apply a very high voltage between the pentavalent tungsten atoms driving voltage as generated element also higher voltage.

On the other hand, FIG. 16 (a) is a conceptual diagram of a state in which the hole 14 through the surface of the nanocrystals is conducted is a diagram showing a conduction hole 14 in the case of nanocrystal structure. The nanocrystal structure, as shown in the figure, since the rutile structure is present with orderliness, has become entire film a fine crystalline, hole conductive manner different from the case of the amorphous film. As described above, the present pentavalent tungsten atom is a surface portion of the nanocrystals 13 with each other, the surface portion is a hole conductive portions. The nanocrystal structure, holes 14 at a low voltage by the surface portion to be the hole conducting portion has a connection is considered to be conductive.

As described above, as the structure of the metal oxide film having good hole conducting properties, (1) that the portion to be a hole conducting portion exists, and, to increase the portion to be a (2) grain boundary Accordingly, it may be necessary to form the overlap of electron orbitals contribute to hole conduction. That is, (1) a metal element in the state of maximum valence less valence than the number of the metal element can take itself exists, (2) a metal oxide film such that the nanocrystal structure, suitable hole conductive structure it can be said that.

Next, we describe a point source of the crystallinity of the tungsten oxide nanocrystals comprising low valence to realize low voltage driving is effective is dominant due to the improvement of hole conductivity. Hole injection layer 4, the hole injection barrier is formed at the interface of the ITO layer 3 and the hole injection layer 4 and the reduction of even driving voltage by reducing the hole injection barrier formed at the interface of the hole injection layer 4 and the buffer layer 6A it is possible to achieve. In the present study, we analyzed the hole conducting energy value using the UPS measurement different shown in Table 3 BPD-D, the tungsten oxide layer produced in the same hole injection layer 4 and the BPD-E of hole conduction efficiency. BPD-D, BPD-E is at a current density of 10 mA / cm 2 as shown in FIG. 4, although the difference of roughly about 2V drive voltage is confirmed, there was no difference in the hole conducting energy value by UPS. That is, difference in the hole injection voltage of BPD-D, BPD-E, the hole injection barrier is formed at the interface of the ITO layer 3 and the hole injection layer 4 and is formed at the interface of the hole injection layer 4 and the buffer layer 6A rather than being formed by the difference of the hole injection barrier, it was confirmed that due to the film structure of the hole injection layer described above.

(For film loss of the hole injection layer)
The present inventors have made sure Hall-only devices HOD-A ~ HOD-E prepared in the above experiments is thinner than immediately after the thickness of the hole injection layer was formed the layer (hereinafter, " to as a film thickness reduction ".) was found to be. This phenomenon, the inventors have reduced film of the hole injection layer was presumed to occur at the bank formation step. Therefore in order to investigate the film thinning phenomenon of the hole injection layer was further subjected to the following confirmation experiments.

As a specific method, to prepare a hole-only devices HOD-a ~ HOD-c for the experiments. Each Hall-only device, a layer made of tungsten oxide to be hole injection layer on a glass substrate was prepared by forming a film by sputtering. Hereinafter referred to as the Hall-only devices HOD-a samples a, sample b Hall-only devices HOD-b, the Hall-only devices HOD-c and sample c. Deposition conditions of sample a ~ c are shown in Table 7. Incidentally, when comparing the deposition condition A in the film forming conditions as in Table 1 of the sample a, the total pressure is different only slightly, both of which are substantially the same conditions.

Prepared samples were a ~ c connected to the DC power supply DC, a voltage was applied. Changing the applied voltage at this time was converted into a value (current density) per unit area of ​​the element value of the current that flowed in accordance with the voltage value. Figure 17 is a device characteristic diagram showing the relationship curve between the applied voltage and the current density of each sample. The vertical axis in the drawing current density (mA / cm 2), the horizontal axis is the applied voltage (V). Than 17, samples a most low drive voltage, the sample b, it can be seen that forward to the driving voltage of c is high. This sample a is high hole conduction efficiency most hole injection layer, the sample b, and the order of c indicates that the small hole conduction efficiency, according to the findings obtained from the first embodiment, the sample a> Sample the amount of order pentavalent tungsten b> sample c means that often.

Next, on the hole injection layer of each sample, the resin material layer having a predetermined resin material (manufactured by Tokyo Ohka Kogyo Co., Ltd. "TFR" series), laminated on the basis of the spin coating method (room temperature, 2500 rpm / 25 sec) , baked (100 ° C., 90 sec) was manufactured through. Then, development processing (TMAH2.38% solution used, development time 60 sec), and cleaning (pure water used, cleaning time 60 sec) was carried out. It was then peeled off the resin material layer. Arrangement and development of the resin material layer, the cleaning process is obtained by assuming the actual bank forming step.

It shows this experimental conditions and results are set forth in Table 7. Further, a graph showing the film density and film reduction amount of the relationship in the table 7 in FIG. 18.

Experimental Results As shown in Table 7, in the sample a hole conducting efficiency was best, the tungsten oxide layer, to a thickness immediately after deposition (80 nm), finally become a thickness of about 23nm It was. Accordingly, the tungsten oxide layer that leads to truly about 57nm about a film thickness amount has been confirmed that lost by film reduction.

Further, as shown in Table 7 and FIG. 18, there is considerable causal relationship between the film thickness reduction amount and the film density of the tungsten oxide layer, it was found that a large film thickness loss as the film density is low. Furthermore, when considering the results of FIG. 17, as the hole transfer efficiency is good, that is, pentavalent film density of greater the amount of tungsten oxide layer of tungsten is low, it can be seen film reduction amount is large. The reason for this will be described with reference to FIG. 19.

Figure 19 is a schematic diagram illustrating the relationship between the film structure and the film density of the tungsten oxide layer constituting the hole injection layer, (a) with any of FIG even hole injection layer formed after the bank formation before the (b) It shows the state. FIG. 19 (a), if the tungsten oxide layer is composed of nanocrystal structure, i.e., a schematic diagram of a hole injection layer when a high hole conduction efficiency, FIG. 19 (b) tungsten oxide layer is amorphous structure (not the entire amorphous, crystal part tungsten oxide to have segregated) when configured for, i.e., it is a schematic view of a hole injection layer is low hole conduction efficiency.

When the hole injection layer of nanocrystals structure (FIG. 19 (a)), which spreads out the grain boundaries of the nanocrystals 13 over the entire region of the hole injection layer, of course, the interface on the side of the bank of the hole injection layer is formed It is spreading the grain boundaries of the nanocrystals 13 also. In this state, a solvent (developer, cleaning solution, etc.) to the hole injection layer is used for forming the bank when exposed, as shown by the arrows in FIG. 19 (a), the interface on the side of the bank is formed solvent entering the hole injection layer through the grain boundary of nanocrystals 13 present. This is because between the grain boundary and the grain boundary of the nanocrystals 13, so to speak so that the gap solvent from entering. Moreover, grain boundaries of the nanocrystals 13, will increasingly route solvent from entering because literally a very fine grain boundaries, the amount of film loss is increased accordingly. Further, as described above, a film having a nanocrystal structure, there is a gap between the grain boundary and the grain boundary of the nanocrystals, the film density is low film.

On the other hand, when the amorphous structure (Figure 19 (b)), the segregated crystal 15 is only present to only a portion of the hole injection layer, the crystal grains become solvent permeating path as indicated by the arrow in FIG. the field is small. Further, since the grain boundaries in the amorphous portion 16 is not connected, as compared with the case of nanocrystal structure, the solvent does not easily penetrating into the deep portion of the hole injection layer (the drawing on the lower side). Therefore, as compared with the case of the nanocrystal structure, believed to film reduction amount decreases. Further, since the film having the amorphous structure is less grain boundaries, voids are not significantly present in the membrane, thus film density becomes high.

From the above experimental results, as the tungsten oxide layer was evaluated with a high hole conduction efficiency in the first embodiment, it was found film thickness reduction amount by the solvent used in forming the banks is large.

However, in general, film reduction thickness of the tungsten oxide layer to result in the above is difficult to manage, also are concerned that there is some effect on the hole conduction efficiency after elements completed. Therefore, if the generation of film loss of such a hole injection layer when the skilled person has become possible to know is assumed to hesitate to constitute a hole injection layer using a tungsten oxide.

However the present inventors have conducted dare end of studying this point intensive, for example, change the development conditions (reducing the developing solution concentration from 2.38% to 0.2% or so), or a change in the baking conditions suitably it is found that can modulate film reduction amount of the tungsten oxide layer. Thus, the inventors have there to be a film thickness can be controlled in the tungsten oxide layer in consideration of the film reduction, a technique according to the regulation of film reduction amount of the hole injection layer and rely, more realistic organic EL device trial studying about, came to check the following technical matters.

As a procedure for Fabrication of organic EL device was formed hole injection layer is first containing tungsten oxide on the anode. The hole injection layer bank material layer on the stacked, performed thereafter, the bank material layer, functional layer exposed predetermined patterned into a shape (this time with an opening for forming a development, each process of washing to). Thereafter, forming a functional layer at a position corresponding to the opening. A cathode was formed on the functional layer.

Here, by applying against the inner surface which includes a corner portion of the ink material recess focuses the corner surrounded by the inner bottom surface and inner surface of the concave portion, constituting the functional layer in the hole injection layer, wetting of the functional layer sex is improved to obtain a knowledge that could form good functional layer.

Therefore the present inventors as shown in the following embodiments, in the region defined in the bank, to form a surface of the functional layer side in the recessed structure, the inner surface of the recess in the recess structure function it is obtained by inspired configured to contact the layer.

Next, a second embodiment will be described focusing on differences from the first embodiment.

[Embodiment 2]
<Schematic Configuration of the organic EL element 100>
Figure 20 is a schematic view showing a stacked state of the layers of the organic EL device 100 according to the second embodiment, FIG. 21 is an enlarged view of a portion surrounded by a dashed line in FIG. 20.

As shown in FIG. 20, the organic EL device 100 according to the second embodiment, red (R), top green (G), and each pixel corresponding to blue (B) are arranged in a matrix or line-like an emission type organic EL device, each pixel has a laminated structure obtained by laminating the layers on the substrate 1.

As shown in FIG. 20, the organic EL device 100 according to this embodiment, the difference is that except for the buffer layer 6A from the organic EL element 1000 according to the first embodiment (FIG. 1). Hereinafter, unless otherwise noted, the materials constituting the layers of organic EL device 100 according to this embodiment is similar to that of the first embodiment.

On the substrate 1, the anode 2 is formed in a matrix or line-like, on the anode 2, ITO layer 3 and a hole injection layer 4 are laminated in this order. Incidentally, ITO layer 3 Whereas is laminated only on the anode 2, the hole injection layer 4 is formed over the upper surface side across the substrate 1 as well as above the anode 2.

On the hole injection layer 4 is formed the bank 5 which defines the pixel, the light emitting layer 6B is laminated in a region defined by the banks 5. Furthermore, on the light-emitting layer 6B, the electron injection layer 7, a cathode 8, and the sealing layer 9 is formed so as to be continuous with that of each neighboring beyond the area defined by the bank 5 pixels .

Region defined by the bank 5, ITO layer 3, the hole injection layer 4, light-emitting layer 6B, and an electron injection layer 7 has a multilayer laminated structure are laminated in this order, functional layer in a stacked structure thereof is It is configured. Note that the functional layer may contain other layers such as a hole transport layer or electron transport layer.

<Structure of each part of the organic EL element 100>
The anode 2 is here has a single-layer structure is formed of Ag (silver). Incidentally, the anode 2 may, for example, formed by APC (silver, palladium, an alloy of copper), ARA (silver, rubidium, gold alloy), MoCr (molybdenum and chromium alloy), NiCr (alloy of nickel and chromium) or the like it may be. For top emission type organic EL element, which is preferably formed of a light reflective material.

ITO layer 3 has a function interposed between the anode 2 and the hole injection layer 4, to improve the bonding of the layers.

Hole injection layer 4 are similar to those of the first embodiment, it is formed by film forming conditions capable of obtaining a good hole conduction efficiency, and a tungsten oxide (WOx) layer. Hole injection layer 4 that is constructed using this material may have a lyophilic property as compared with the surface of the bank 5.

(For the hole injection layer 4)
Here, as shown in FIG. 21, the hole injection layer 4, as well has spread along the bottom surface of the bank 5 in the pixel direction next, and subsidence than the level of the bank 5 bottom in the region defined by the banks 5 It is formed in a recessed structure, comprising a predetermined dissolved by solvent recess formed 4a (portion indicated by hatching in mesh in FIG. 21). The hole injection layer 4 is, only the area defined by the bank 5 has a film thickness in comparison with other regions thinner, the thickness of the other region is substantially uniform throughout. Since the hole injection layer 4 is a metal compound having a lyophilic, the inner surface 4b of the recessed portion 4a is a good wettability with respect to ink. Accordingly, easily fit into the inner surface 4b of the ink recess 4a which is dropped to a defined area in the bank 5, easily remains in the ink is defined by the banks 5 region.

Incidentally, the hole injection layer 4 may be any recess structures subsidence than the level of the edge portion 5a of the bottom surface of the at least bank 5 need not be a recess structure in which subsidence than the level of the entire bottom surface. In the present embodiment has been sinking below the level of the edge 5a of the bottom surface, but has a recess structure that is not sinking below the level of the central portion 5b of the bottom, for example, two-dot chain line in FIG. 21 as shown by 5c, align the level of the bottom surface of the bank of the central portion 5b in the edge portions 5a, and the like to flatten the bottom surface of the bank 5, even recessed structure in which subsidence than the level of the entire bottom surface of the bank 5 good.

Hole injection layer 4 is a concave structure sunk from the lower edge 5d corresponding sites of banks, specifically, the substrate defined area in the bank 5 in the upper surface of the hole injection layer 4 from the lower edge 5d corresponds site It is sunk in a substantially vertically downward with respect to the first top surface. Thus, if a recess structure that sinks from the lower edge 5d corresponding sites of banks 5, over the thickness of the light-emitting layer 6B in a wide range can be made uniform, luminance unevenness in the light emitting layer 6B is unlikely to occur .

Incidentally, the hole injection layer 4 is not limited to the recess structures subsidence from the lower edge 5d corresponding sites of banks 5, for example, as shown in FIG. 22, next to the pixel side than the lower end edge 5d corresponding sites of banks 5 it may be subsidence structure from the closer sites. Further, it may be a recessed structure in which subsidence from sites closer to the pixel center side than the lower end edge 5d corresponding sites of the bank 5, the contour of the recess 4a when its as indicated by a two-dot chain line 10 in FIG. 22 a shape.

Further, recessed structure of the hole injection layer 4 is a cup-shaped, and more specifically, the inner surface 4b of the recessed portion 4a is brought into contact with the bottom surface 6a of the light-emitting layer 6B a substantially parallel and planar and the upper surface of the substrate 1 a bottom surface 4c among which extends toward the edge of the inner bottom surface 4c on the upper surface and substantially perpendicular direction of the substrate 1, and a inner surface 4d in contact with the side surface 6b of the light-emitting layer 6B. Thus, if recess structure is cup-shaped, since the ink in the recess 4a by the presence of the inner side surface 4d is less likely to move to the surface parallel to the upper direction of the substrate 1, the region defined by the banks 5 ink can be kept more stably kept the. Moreover, when the recessed structure into a cup shape, the area of ​​the inner surface 4b of the recessed portion 4a is increased, the area in close contact between the ink and the hole injection layer 4 is increased, more stable ink in the region defined by the banks 5 it is possible to be kept to. Therefore, it is capable of high definition patterning of the light-emitting layer 6B.

Incidentally, the re-entrant structure of the hole injection layer 4 is not limited to a cup shape, as shown in FIG. 23, for example (indicated by hatching in mesh 23) cross-sectional shape of the recess 4a is substantially fan or substantially inverted triangle, etc. it may be a dish shape that is.

Returning to FIG. 21, the average depth t of the recess 4a is not particularly specified in the present invention, it can be, for example, 5 ~ 100 nm. When the average depth t of the recess 4a is 5nm or more, it is possible to accumulate a sufficient amount of ink in the recess 4a, the ink can be kept to stably in the region defined by the banks 5. Furthermore, since it is formed without the light-emitting layer 6B to the bank 5 end is repelled, it is possible to prevent a short circuit between the electrodes 2,8.

The average depth t of the recess 4a measures the surface contour of the hole injection layer 4 at a stylus profilometer or AFM (atomic force microscope), an average height and valley portions which become peaks of the surface profile and it obtains the difference between the average height of the portion to be, can be obtained.

On the other hand, is not particularly specified in the thickness of the light-emitting layer 6B, for example, if the average depth t of the recess 4a when the average film thickness h after drying of the light-emitting layer 6B is not less than 100nm is at 100nm or less, it can be made uniform thickness of the light-emitting layer 6B at a defined area bank 5.

Further, it is preferred that a difference between the average depth t of the average film thickness h and the recess 4a of the light-emitting layer 6B is 20nm or less. If the average film thickness h of the light emitting layer 6B is too small than the average depth t of the recess 4a is (for example, in the case of t-h> 20 nm), as shown in FIG. 24 (a), the inner surface of the concave portion 4a 4d portion not in contact with the light-emitting layer 6B (part of the light-emitting layer 6B is uncoated) occurs, there is a fear that short circuit between the electrodes 2,8 is generated at that portion. The average thickness h of the light emitting layer 6B is if too large than the average depth t of the recess 4a (e.g., in the case of h-t> 20 nm), as shown in FIG. 24 (b), the bank 5 the film thickness of the bank portion near 6c of the light-emitting layer 6B with liquid repellency becomes thinner than other portions, so the cross-sectional shape of the light-emitting layer 6B is a Ryakutotsugata, uneven light emission occurs due to the difference in thickness I fear there is.

Incidentally, the inner surface 4d of the recess 4a is sufficient if in contact with at least a portion of the side surface 6b of the light-emitting layer 6B. For example, average film thickness h of the light emitting layer 6B as shown in FIG. 21 and FIG. 24 (b) is greater than the average depth t of the recessed portion 4a, or, if they are the same size, the light emitting layer 6B the inner surface 4d of only the recess 4a is downward at least part of the side surface 6b contacts. On the other hand, when the average film thickness h of the light emitting layer 6B as shown in FIG. 24 (a) is smaller than the average depth t of the recess 4a, the inner surface 4d of the recess 4a on the entire side surface 6b of the light-emitting layer 6B There is contact.

As shown in FIG. 25, in the recess 4a of the hole injection layer 4, for example, a hole transport layer that constitutes the functional layer lyophilic layer 12, such as IL layer (intermediate layer), under the light-emitting layer 6B it may be formed on the side. In this case, although will be ink on the upper surface 12a of the lyophilic layer 12 rather than the inner bottom face 4c of the concave portion 4a is dropped, still for the upper surface 12a is lyophilic, defined by the banks 5 region ink can be kept stably in. However, since the inner surface 4d of the recess 4a recess 4a by lyophilic layer 12 will completely filled is no longer in contact with the ink, the average thickness g of the lyophilic layer 12 is the average of the recess 4a it is preferably thinner than the depth t.

Note that lyophilic layer 12 is a layer of thickness of about 10 nm ~ 20 nm, has a function of transporting into the light emitting layer 6B the holes injected from the hole injection layer 4 (hole). The lyophilic layer 12, using a hole transporting organic material. The hole transporting organic material is an organic substance having a property of transmitting the charge transfer reaction between the holes resulting molecule. This is sometimes referred to as p- type organic semiconductor.

Lyophilic layer 12 may be a low molecular material in the polymeric material is deposited in a wet printing method. When forming the light-emitting layer 6B is an upper layer, so that hardly eluted into this preferably contains a crosslinking agent. Examples of hole-transporting materials can be used triarylamine derivative copolymer and a low molecular weight having a fluorene moiety and triarylamine site. Examples of the crosslinking agent, or the like can be used dipentaerythritol hexaacrylate. In this case, poly doped with polystyrene sulfonate (3,4-ethylenedioxythiophene) (PEDOT-PSS) and, it is preferable that formed at its derivative (copolymer or the like).

Bank 5 has an insulating property is formed of an inorganic material such as an organic material or glass resin. Examples of the organic material, an acrylic resin, polyimide resin, include novolac type phenol resin, examples of the inorganic materials, SiO 2 (silicon oxide), Si 3 N 4 (silicon nitride) or the like can be mentioned It is. Bank 5 preferably has an organic solvent resistance, also it is preferable to appropriately transmitting some visible light. Further, the bank 5 the etching process, because it may baking or the like is, is preferably formed of a high resistance to their treatment material.

Bank 5 is at least the surface of liquid repellency. Therefore, when forming the bank 5 in lyophilic material is equality the surface subjected to water repellent treatment must be liquid-repellent.

Further, the bank 5 may be pixels bank, may be a line bank. If a pixel bank, the bank 5 is formed so as to surround the entire circumference of the pixels for each light emitting layer 6B. On the other hand, in the case of line banks, the bank 5 to delimit a plurality of pixels for each or each matrix are formed, the bank 5 is present only in the row direction on both sides or column on both sides of the light-emitting layer 6B, the light-emitting layer 6B is same column or bank of what is a continuous structure.

Electron injection layer 7 has a function of transporting electrons injected from the cathode 8 to the light-emitting layer 6B, for example, barium, phthalocyanine, lithium fluoride, be formed by a combination thereof or the like.

Cathode 8 is here formed with a single layer structure using, for example, ITO, IZO (indium zinc oxide) or the like. For top emission type organic EL device, it is preferably formed of a light transmissive material.

The sealing layer 9, or the light emitting layer 6B and the like are exposed to moisture, has a function of suppressing it or exposed to air, for example, SiN (silicon nitride), a material such as SiON (silicon oxynitride) It is formed. For top emission type organic EL device, it is preferably formed of a light transmissive material.

<Method of manufacturing the organic EL element 100>
Figure 26 is a process diagram illustrating the method of manufacturing the organic EL device 100 according to the second embodiment, FIG. 27 is a process diagram illustrating the method of manufacturing the organic EL device 100 which is subsequent to FIG. 26.

In the manufacturing process of the organic EL device 100, first, as shown in FIG. 26 (a), the matrix by the Ag thin film is formed by, for example, sputtering on the substrate 1 made of glass, patterning the Ag thin film for example by photolithography Jo or line shape to form the anode 2. Incidentally, Ag thin film may be formed by vacuum deposition or the like.

Next, as shown in FIG. 26 (b), for example, an ITO film was formed by sputtering to form an ITO layer 3 by patterning the ITO film by, for example, photolithography.

Subsequently, a thin film 11 containing metal compound is soluble for a given solvent. For example, by using a composition comprising a WOx or MoWOx, vacuum deposition method, the sputtering method, so that a uniform film thickness over the upper surface side across the substrate 1 to form a thin film 11 of WOx or MoWOx.

Next, as shown in FIG. 26 (c), for example, forming a bank 5 to surround each pixel region (region where the anode 2 is arranged) by photolithography. In that case, for example, by coating or the like on the thin film 11 comprises a resist material as the bank material, a resist film (for example, a resin film) as a bank film, a resist pattern is formed on the further the resist film, then developer by forming a pattern of banked 5 remove the desired portions of the resist film by etching. In the case of forming the bank 5 in inorganic materials, for example, a CVD method, or the like. Resist residues adhering to the surface of the remaining film 11 after etching is removed, for example, hydrofluoric acid. Moreover, subjected to liquid-repellent treatment on the surface of the bank 5 as necessary.

Next, as shown in FIG. 26 (d), the hole injection layer 4 to form a recess 4a by dissolving a portion of the thin film 11. Thus, the hole injection layer 4 is, only the area defined by the bank 5 becomes small film thickness structure than other regions. Formation of the recess 4a, for example, impurities such as hydrofluoric acid remaining on the bank 5 surface after the resist residue removal during pure water cleaning for cleaning with pure water is defined by the bank 5 in the thin film 11 the top surface in its pure water It was carried out by dissolving the area. In that case, the predetermined solvent is pure water, the depth and shape of the recess 4a may be appropriately adjusted by changing the conditions of the pure water washing.

As a specific method, for example, advance the substrate 1 is rotated at a spin coater and washed dropped pure water (e.g., room temperature) on the substrate 1 being rotated. Then, turn off the water to stop from dripping pure water while continuing to rotate the substrate 1. In this case, the time for dripping pure water is adjustable depth and shape of the recess 4a. Also, dissolution rate of the thin film 11 because also vary with the temperature of the pure water, it is also possible to adjust the depth and shape of the recess 4a by the temperature of the pure water.

The method of forming the recess 4a is not limited to the above. For example, after forming the bank 5, the washing with washing liquid such as pure water resist residues adhering to the surface of the thin film 11, even if a recess 4a by dissolving a portion of the thin film 11 by the cleaning solution good. In that case, the predetermined solvent is washing liquid. Further, the resist film to form a bank 5 is etched by the developing solution, the developing solution by washing the resist residues adhering to the surface of the thin film 11, and the recess 4a by dissolving a portion of the thin film 11 formed may be. In that case, the developer is a predetermined solvent.

When forming the hole injection layer 4 to dissolve the thin film 11 by using a solvent such as cleaning liquid and the developing solution used in the bank formation process, there is no need to use separately predetermined solvent to form a recess 4a in addition, the order is not necessary to perform additional process for forming the recess 4a, the production efficiency is good.

The formation of the recess 4a is not limited to the case of using the predetermined solvent, for example, firstly, sputtering and the WOx or MoWOx thin in all areas where the anode 2, except the arrangement region by using photolithography formed by forming a thin film of WOx or MoWOx all areas thereon may be performed at equal other ways of forming a concave hole injection layer 4 in a region where the anode 2 is arranged.

Next, as shown in FIG. 27 (e), the ink was dropped into the region defined by the bank 5, for example by an ink jet method, along with the ink on the inner bottom surface 4c and inner surface 4d of the hole injection layer 4 coated and it is dried to form a light emitting layer 6B with. Note that a dispenser method, a nozzle coating method, a spin coating method, intaglio printing, ink may be dropped by letterpress printing or the like.

Next, as shown in FIG. 27 (f), for example, to form a barium thin film serving as an electron injection layer 7 by vacuum evaporation, as shown in FIG. 27 (g), an ITO thin film as the cathode 8 by sputtering, for example formed and, as shown in FIG. 27 (h), further forming a sealing layer 9.

[Embodiment 3]
The organic EL device 100A according to the third embodiment are that no ITO layer is formed under the hole injection layer, and in that the protective film on the hole injection layer is formed, according to the second embodiment very different from the organic EL element 100. Hereinafter, it focuses on the differences from the second embodiment, the information about a point as in the second embodiment simplified or omitted to avoid repetition.

<Configuration of the organic EL device 100A>
Figure 28 is a schematic view showing a stacked state of the layers of the organic EL device 100A. The organic EL element 100A as shown in FIG. 28 is an anode 102 is formed as an anode on the substrate 101, the hole injection layer 104 and the protective layer 110 as a charge injection transport layer on are laminated in this order ing. Incidentally, while the hole injection layer 104 is formed over the entire upper surface of the substrate 101, the protective layer 110 is not formed over the anode 102. Further, ITO layer between the anode 102 and the hole injection layer 104 is not interposed.

The on the hole injection layer 104 and the bank 105 for partitioning the pixel is formed, the light-emitting layer 106B are stacked in zoned areas in the bank 105, on the light-emitting layer 106B, the electron injection layer 107, the cathode there cathode 108 and sealing layer 109 is formed so as to be continuous with that of each beyond a region defined by the bank 105 next pixel.

<The method for manufacturing an organic EL device 100A>
Figure 29 is a process diagram illustrating the manufacturing method of the organic EL device 100A. In the manufacturing process of the organic EL device 100A, first, as shown in FIG. 29 (a), an anode 102 is formed of a material Al (aluminum) based on the substrate 101 made of glass, on which a hole injection layer after the WOx or MoWOx thin film 111 serving as 104 formed further thereon, after forming the WOx or MoWOx thin film 112 serving as a protective layer 110. The thin film 112 has a function of protecting the hole injection layer 104 during the etching for the bank 105 is formed.

Next, as shown in FIG. 29 (b), forming a bank 105 on the thin film 112. Specifically, a resist film is formed comprising a resist material on the thin film 112, further forming a resist pattern on the resin film, then developing solution by removing the desired portion of the resist film by etching, the bank forming a pattern of 105. The impurity of the remaining hydrofluoric acid or the like to the bank 105 surface after forming is removed and washed with washing liquid such as pure water, defined area in bank 105 in the top surface of the thin film 112 by the cleaning liquid subsidence melt.

Furthermore, as shown in FIG. 29 (c), continuing the treatment with the cleaning solution, any defined area in the bank 105 of the thin film 112 is in a state of the protective layer 110 melted. Then, to expose the thin film 111 by the thin film 112 is melted, and subsidence melts a region defined by the bank 105 in the upper surface of the thin film 111, the recess 104a is formed. Such a hole injecting layer 104 is formed as described above.

Next, as shown in FIG. 29 (d), to form the luminescent layer 106B in a region defined by the bank 105. Subsequent steps is omitted because it is same as the process according to the second embodiment.

[Embodiment 4]
The organic EL device 100B according to the fourth embodiment, the region where the hole injection layer is formed is very different from the organic EL device 100A according to the third embodiment. Hereinafter, focuses on differences from the third embodiment, the information about a point as in the third embodiment is simplified or omitted to avoid repetition.

<Structure of the organic EL element 100B>
Figure 30 is a schematic view showing a stacked state of the layers of the organic EL element 100B. The organic EL element 100B as shown in FIG. 30, the anode 202 is an anode on a substrate 201 is formed, the hole injection layer 204 and the protective layer 210 as a charge injection transport layer on are laminated in this order ing. Hole injection layer 204 is not formed over the entire upper surface of the substrate 1, it is formed only in the peripheral portion of the anode 202 and over the anode 202. On the other hand, the protective layer 210 is not formed over the anode 202.

The on the hole injection layer 204 is formed with a bank 205 for partitioning the pixel, the light emitting layer 206B is stacked zoned area in the bank 205, on the light-emitting layer 206B, the electron injection layer 207, the cathode there cathode 208 and sealing layer 209 is formed so as to be continuous with that of each beyond a region partitioned by the bank 205 next pixel.

<Method of manufacturing an organic EL element 100B>
Figure 31 is a process diagram illustrating the manufacturing method of the organic EL element 100B. In the manufacturing process of the organic EL element 100B, first, as shown in FIG. 31 (a), an anode 102 is formed of Al-based material on the substrate 101 made of glass, then the exposed surface of the anode 102 (the upper surface and forming an oxide film 211 serving as the hole injection layer 204 by oxidizing a side surface), further thereon, after forming the protective layer 210 to become WOx or MoWOx thin film 212.

Next, as shown in FIG. 31 (b), forming a bank 205 on the thin film 212. Impurities such as hydrofluoric acid remaining on the bank 205 surface was washed with washing solution such as pure water is removed, but defined area in the bank 205 of the thin film 212 upper surface by the cleaning liquid subsidence melt.

Furthermore, as shown in FIG. 31 (c), continuing the treatment with the cleaning solution, the thin film 212 is in a state of the protective layer 210 is a final form melts all region defined by the bank 205. Further, since the exposed area defined by the bank 205 of the oxide film 211 by the thin film 212 is melted, even sunken melts the upper surface of the region, the recess 204a is formed. Hole injection layer 204 in this manner is formed.

Next, as shown in FIG. 31 (d), to form the luminescent layer 206B in a region defined by the bank 205. Subsequent steps is omitted because it is same as the process according to the second embodiment.

[Embodiment 5]
Figure 32 is a perspective view showing an organic EL display device or the like according to the fifth embodiment. As shown in FIG. 32, the organic EL display device 300 according to one embodiment of the present invention, R, G, or each pixel for emitting light of B are regularly arranged in a matrix in row and column directions comprising a comprising organic EL panel, each pixel is composed of an organic EL device according to an embodiment of the present invention.

[Modification]
Having described Embodiments 1 to Embodiment 5 of the embodiment, the present invention is not limited to these embodiments. For example, modifications are possible as follows.

(1) In the first embodiment, is shown as an example tungsten oxide layer was deposited by DC sputtering as a hole injection layer, a film forming method and oxide metal species is not limited thereto. Other example deposition method as a deposition method, CVD method, and the like. Further, in the above embodiment, an example has been described that constitutes the hole injection layer by tungsten oxide, in addition to tungsten trioxide, for example, molybdenum oxide (MoOx), molybdenum - tungsten oxide (MoxWyOz) metal oxides such as object, even when a metal nitride or metal oxynitride, it is possible to achieve the same effect.

(2) organic EL device according to an embodiment of the present invention is not limited to the configuration using a device with a single. A plurality of organic EL elements by integration on the substrate as a pixel, it is also possible to configure the organic EL light-emitting device. The organic EL light-emitting device may be embodied by setting the film thickness of each layer in each of the elements appropriately, for example, it can be utilized as a lighting device or the like.

(3) In the above embodiments, comprising 15, the rising position of the peak P1, FIG. 15 (a2), and the differential intensity 0 in the beginning toward the center point of the peak top of the peak P1 in (b2) was the point. Method of determining the rise position of the peak P1 is not limited to this. For example, to describe an example graph (a1) of FIG. 15, the average value of the normalized luminance in the vicinity of the rising position of the peak P1 and the baseline, that the intersection between the base line and the peak P1 and the rising position of P1 It can also be.

(4) In the above embodiment has been described in the top emission type is not limited thereto and may be a bottom emission type.

(5) In the above embodiment, only the electron injection layer between the light emitting layer and the cathode is interposed, or may be inserted through the electron transport layer in addition thereto.

The organic EL device of the present invention, for example, household or public facilities, or various display devices for business, television set, it is suitably used in an organic EL device used in portable electronic devices for display.

1,101 board 2, 102, 202 anode 3 ITO layer 4,104,204 level 5d of the bottom surface of the bottom surface 5c banks of the inner surface 5, 105, 205 banks 5a bank of the inner bottom surface 4d recess of the hole injection layer 4a recess 4c recess bank of the lower edge 6A buffer layer 6B, 106B, 206B emitting layer 6a emitting layer of the bottom surface 6b side 7 electron injection layer 8,108,208 cathode 8A cathode of the light emitting layer (gold layer)
9 sealing layer 13 Nanokuritaru 14 holes 15 segregated crystals 16 amorphous portion 300 display 1000,100A, 100B organic EL element 1000A Hall-only device DC power supply

Claims (23)

  1. And the anode,
    And a cathode,
    Disposed between the anode and the cathode, including a light emitting layer formed using an organic material, a functional layer comprising one or more layers,
    A hole injection layer disposed between the anode and the functional layer,
    And a bank defining the light-emitting layer,
    The hole injection layer comprises a tungsten oxide,
    The tungsten element constituting the tungsten oxide is contained in the hole injection layer at a lower valence state than hexavalent state and the hexavalent and
    The hole injection layer comprises a particle size of the tungsten oxide is a size of nanometer order crystal,
    In the above-defined region in the bank is formed in a recessed structure portion of the surface of the functional layer side is positioned on the anode side than the other portions,
    The organic EL element characterized in that the inner surface of the recess in the recess structure is in contact with the functional layer.
  2. The lower valence than divalent 6, the organic EL device according to claim 1, wherein the pentavalent.
  3. The atomic number of the pentavalent tungsten element, to claim 2 wherein said hexavalent W 5+ / W 6+ is divided by the number of atoms of the tungsten element, characterized in that at 3.2% or more the organic EL element described.
  4. The organic EL device according to claim 3, wherein the W 5+ / W 6+ is 7.4% less than 3.2%.
  5. Claims in hard X-ray photoelectron spectrum of the hole injection layer surface, wherein the second peak exists in a low binding energy region than the first peak corresponding to the 4f 7/2 level of hexavalent tungsten the organic EL device according to claim 1.
  6. The second peak, the organic EL device according to claim 5, characterized in that present in the 0.3 ~ 1.8 eV lower binding energy region than the binding energy value of the first peak.
  7. The integrated intensity of the second peak, the relative integrated intensity of the first peak, 3.2 organic EL according to any one of claims 5 and 6, characterized in that the - 7.4% element.
  8. Wherein the presence of a low valence state of the tungsten element than hexavalent, the band structure of the hole injection layer, than the lowest binding energy valence band to 1.8 ~ 3.6 eV lower binding energy region the organic EL device according to any one of claims 1 to 7, characterized in that it has an occupancy level.
  9. The hole injection layer, an organic EL element according to any one of claims 1 to 8, wherein the particle size include a plurality of 3 to 10 nanometers in size is the tungsten oxide crystal.
  10. In the lattice image by transmission electron microscopy of the hole injection layer section, claims 1 to any one of 9, characterized in that appear regularly arranged linear structures at intervals of 1.85 ~ 5.55A the organic EL device according to item.
  11. Wherein in the two-dimensional Fourier transform image of lattice image, the organic EL device according to claim 10, characterized in that the concentric pattern around the center point of the two-dimensional Fourier transform image appears.
  12. In the plot representing the distance from the center point, the relationship between the normalized luminance is a value obtained by normalizing the luminance of the two-dimensional Fourier transform image of said distance, characterized in that the peak of the normalized luminance appears one or more the organic EL device according to claim 11,.
  13. Said distance corresponding to the position of the peak of the normalized luminance appearing closest from the center point in the plot, the difference between the distance corresponding to the rising position of the peak of the normalized luminance as a peak width,
    Said distance corresponding to the center point, and wherein the peak width when the difference between the distance and 100 corresponding to the peak of the normalized luminance appearing closest from the center point is less than 22 the organic EL device according to claim 12,.
  14. The functional layer is an organic EL element according to any one of claims 1 to 13, characterized in that it comprises an amine-based material.
  15. The functional layer, the hole transport layer for transporting holes, according to any one of claims 1 to 14, characterized in that either of the buffer layer used in applications adjustment or electron blocking optical properties the organic EL element.
  16. The bank is lyophobic, organic EL element according to claim 1, wherein the hole injection layer is lyophilic.
  17. The organic EL panel comprising an organic EL element according to any one of claims 1 to 16.
  18. The organic EL light-emitting device comprising an organic EL element according to any one of claims 1 to 16.
  19. The organic EL display device comprising the organic EL element according to any one of claims 1 to 16.
  20. An anode preparation step of preparing an anode,
    A tungsten oxide film forming step of forming a tungsten oxide layer on the anode, sputtering gas composed of argon gas and oxygen gas, and, using a target made of tungsten, the total pressure of the sputter gas is more than 2.3Pa with 7.0Pa or less, wherein it is the ratio of the oxygen gas partial pressure to the total pressure of the sputtering gas is 50 to 70%, and applied power density is closing electric power per unit area of ​​the target 1 .5W / cm 2 or more 6.0 W / cm 2 or less, and the total pressure / input power density which is a value obtained by dividing the total pressure in the input power density of the sputtering gas is from 0.7 Pa · cm 2 / W a tungsten oxide film forming step of forming a tungsten oxide layer is large deposition conditions,
    On the tungsten oxide layer, a resist film is formed comprising a resist material, etching treatment with a developer, a bank forming step of forming a bank,
    After forming the banks, the resist residues adhering to the tungsten oxide layer surface with washing with a cleaning solution, the cleaning solution in dissolving a portion of the tungsten oxide layer, a portion of the upper surface than other portions of the upper surface a hole injection layer forming step of forming a hole injection layer also having a recess and a inner surface located on the anode side, continuous to the inner bottom surface and the inner bottom surface,
    Ink was added dropwise to have been within the region defined by the banks, coated and dried so as to contact with the ink on the inner surface of the concave portion of the hole injection layer, a functional layer formation step of forming a functional layer,
    Method of manufacturing an organic EL element characterized by having, a cathode forming step of forming the cathode above the functional layer.
  21. An anode preparation step of preparing an anode,
    A tungsten oxide film forming step of forming a tungsten oxide layer on the anode, sputtering gas composed of argon gas and oxygen gas, and, using a target made of tungsten, the total pressure of the sputter gas is more than 2.3Pa with 7.0Pa or less, wherein it is the ratio of the oxygen gas partial pressure to the total pressure of the sputtering gas is 50 to 70%, and applied power density is closing electric power per unit area of ​​the target 1 .5W / cm 2 or more 6.0 W / cm 2 or less, and the total pressure / input power density which is a value obtained by dividing the total pressure in the input power density of the sputtering gas is from 0.7 Pa · cm 2 / W a tungsten oxide film forming step of forming a tungsten oxide layer is large deposition conditions,
    Above the tungsten oxide layer, a resist film is formed comprising a resist material, etching treatment with a developer, to form a bank, was washed resist residues adhering to the tungsten layer surface by the developer, and, the cleaning solution by dissolving a portion of the tungsten oxide layer, the recess having an inner surface portion of the upper surface than other portions of the upper surface located on the anode side, continuous to the inner bottom surface and the inner bottom surface a hole injection layer forming step of forming a hole injection layer having,
    Ink was added dropwise to have been within the region defined by the banks, coated and dried so as to contact with the ink on the inner surface of the concave portion of the hole injection layer, a functional layer formation step of forming a functional layer,
    Above the functional layer, the manufacturing method of the organic EL element characterized in that it has a cathode forming step of forming a cathode, a.
  22. In the tungsten oxide film formation step,
    Tungsten element forming the tungsten oxide layer is such that said elemental tungsten is contained in the tungsten oxide layer at the maximum valence state and the maximum valence lower valence than the number of possible states, and the particle size to include crystals of a size which tungsten oxide of nanometer order, the organic EL device according to any one of claims 20 or claim 21, characterized in that depositing the tungsten oxide layer Production method.
  23. The tungsten oxide film formation step, the total pressure / organic EL element according to any one of claims 20 or claim 21 input power density is equal to or less than 3.2 Pa · cm 2 / W the method of production.
PCT/JP2010/004992 2010-08-06 2010-08-06 Organic electroluminescence element and method of manufacturing thereof WO2012017502A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2010/004992 WO2012017502A1 (en) 2010-08-06 2010-08-06 Organic electroluminescence element and method of manufacturing thereof

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